DE2430998A1 - NEW ORGANIC COMPOUNDS CONTAINING AN N, N-DIALKYL-SUBSTIBUTED AMIDE GROUP AND METHOD OF PREPARING THEREOF - Google Patents

Description

The invention relates to new organic compounds, which are valuable in a wide range of applications are, for example, as surfactants for non-aqueous media, as a dispersant for aqueous Media, as a solvent, as a chelating agent or as a modifier for high molecular weight compounds that have various improved properties such as hydrophilicity; Softness, anti-static properties ten, adhesion or plasticity for compounds of high molecular weight and molded articles manufactured therefrom ertsilen and a method for producing such new organic compounds. ;

In particular, the invention relates to new organic ones Compounds of the following formula (1) with the above indicated usability

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^ fCOCH ₂ CH ₂ O

(D

wherein A is a group from the classes of the monovalent to hexavalent hydrocarbon groups, monovalent to hexavalent organic groups with an ether linkage chain and monovalent to subvalent organic groups which result from the connection of an alkylene group or a polyether linkage chain to the bond of a member from the group of -OH, ->H,> 1IH and> 1TR, where R is an alkyl group, give R. and R ₂ alkyl groups with 1 Ms 4 carbon atoms, B hydrogen atoms, alkyl groups or hydroxyalkyl groups, m the number 0, 1 or 2, η is an integer from 2 to 6, if m is the number O, and O, 1 or 2, if m is the number 1, and 0, if m is the number 2, while ρ is the number 0 or 1, and a process for their manufacture.

Dimethylformamide, diethylformamide, dimethylacetainide and hexamethylphosphorylamide are known compounds which contain an H, F-dialkylamide group. These connections are all called "super-solvents" since they possess superior resolving power and affinity for show a wide range of substances. These compounds can be used as solvents having unique solvent power, but cannot be used as surface active agents, dispersants, chelating agents and modifiers be used for high molecular weight compounds.

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It is known that dimethylformamide or hexamethylphosphoramide sometimes act as anti-damage agents for polymers. However, they are super solvents They are compounds with relatiy low boiling point and due to their poor thermal stability unsuitable as additives for the treatment of polymers. In fact, they were rarely used in technical practice.

- Since all of the above super-solvents have a NjN-dialkyl-substituted amide group, Compounds with a ΪΤ, Ν-dialkyl-substituted amide group sought that might be useful for the various additives listed above.

In US Pat. No. 2,372,808 compounds are described which by addition reaction between polyhydric alcohols and acrylamide can be obtained. These compounds are used as plasticizers for nitrocellulose, Cellulose acetate, ethyl cellulose, vinyl chloride resins, polyvinyl acetal resins, phenolic resins * acrylic resins and PMMM resins are used. In this US patent There is no reference to any connections whatsoever of formula (1). Because the amide bond of N-unsubstituted Amide compounds such as acrylamide described in this patent are prone to cleavage by acids or alkalis, there are many complicated ones and disadvantageous restrictions on the reaction conditions, to avoid this. Furthermore, since carboxyl groups are formed in the reaction product, they change its properties. In this UB patent compounds used with an H-unsubstituted Amide groups have two active hydrogen atoms that are tied to the IT atom and they have a strong Adhesive strength and high hydrogen bonding capacity. Therefore, they have a relatively good compatibility with hydrogen-containing compounds, but have one poor affinity for a wide range of compounds

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fertilize. Therefore, the compounds shown in US Pat. No. 2,372,808 differ greatly from the novel compounds according to the invention in terms of molecular structure, properties and uses.

One object of the invention is new organic ones Compounds which are used in a wide range of applications, for example as surface-active agents, as a dispersant, as a chelating agent or as a modifier for polymer compounds and molded articles from this are valuable.

Another object of the invention is a process for the preparation of these new organic compounds.

Another object of the invention is a resin composition containing such novel organic compounds contains.

Numerous other objects and advantages of the invention will become apparent from the following description.

Among the compounds of the formula (1), compounds of the formula (1a) are preferred:

* 2

there)

ra

where A is a group from the classes from monovalent to hexavalent saturated aliphatic hydrocarbons, monovalent cycloalkyl - ^ - or divalent cycloalkylene groups, monovalent to hexavalent polyalkylene glycol residues and monovalent to hexavalent organic groups resulting from bonding an alkylene group or a Polyalkylene glycol having an alkylene group of 2 to 4

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Carbon atoms. "- to the bond of one of the groupings -OH,> $! -,> ΪΓΗ and> NR, where JS .. represents an Alley! Group with 1 to 20 carbon atoms, IL and Ip Alky! groups with 1 to 4 carbon atoms, B hydrogen atoms, alky groups with 1 to 10 carbon atoms or hydroxyl groups with 1 to 3 carbon atoms, m the numbers Oy 1 or 2, η the numbers 2 to 6, if m had the value 0 , and 0, -1 or 2 if m has the value 1, and 0 if m has the value 2, and ρ denotes the numbers 0 or 1..

The compounds of the formula (1a) are compounds in which A is a group from the class of monovalent to hexavalent saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, monovalent Gc- or Cg-cycloalkyl or divalent C ₁ - or Cg- Gycloalkylene groups, monovalent to hexavalent polyalkylene glycol radicals with an alkylene group with 2 to .4 carbon atoms and monovalent to hexavalent organic groups, ¹ derived from the compound of an alkylene group with 2 to 4 carbon atoms or a polyether bond chain derived from a polyalkylene glycol with an alkylene group having 2 to 4 carbon atoms, on the bond of a grouping -OH, ->ΪΓ,> NH and> NR, in which R is an alkyl group having 1 to 20 carbon atoms, are obtained, is particularly preferred.

Preferred examples of group A are:

e invalid; ; GH ₃ -, C ₂ H ₅ -, C ₄ H ₉ -, C ₈ H ₁ ^ -, C ₁ ^ ₁₅ - , C ₁ 3H _3? -

.- ■■■ '■ V -U- 1' ■■■: .ψτ . ■. ":.

divalent ;. -CHgCH ₂ - ,; -CH ₂ CH ₂ CH ₂ -, -CH ₂ -CH-, -

CHpCHpCHCHt

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CH ₅

ι ^d ι

trivalent: -CH ₂ -C-CH ₂ CH ₃ -, -CH ₂ -CH-CH ₂ -,

OH ₂

OH,

-CH ₂ CH ₂ -C-CH ₂ CH ₂ -, -CH ₂ -C-CH ₂ -

x ^c - \ ι

tetravalent: -CH ₂ -C-CH ₂ -, -CH ₂ -CH-CH-CH ₂ -

CH ₅

• ■ ·

ι ι t

pentavalent: -CH ₂ -CH-CH-CH-CH ₂ -

I I I t

hexavalent: -CH ₂ -Ch-CH-CH-CH-CH ₂ -

Examples of monovalent cycloalkyl or divalent cycloalkylene groups having 5 or 6 carbon atoms are e.g.

/ ^GH2 X S CH-, -CH

Examples of monovalent "to hexavalent polyalkylene glycol radicals with alkylene groups of 2 to 4 carbon atoms are there B.

-CH ₂ GH ₂ OGH ₂ GH ₂ -, 4GH ₂ CH ₂ O ^ CH ₂ CH ₂ -, -4 GK ₂ CE ₂ O ^ CE ₂ CK ₂ -

- (CK ₂ GE ₂ O ^ CH ₂ CE ₂ -, ^} Ii2GH ₂ 0 ^ CH2GH2- _^ - ^ H ₂ CH ₂ O

CH3 CH3

CH3

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4C ₃ K ₆ ) -04CE ₂ CiI ₂ CH ₂ CH ₂ -0> ^ - g (CH ₂ Ij- ■

CH ₃ CH ₃

-H CH ₂ -O ^ CH ₂ CH ₂ - GH ₂ - (OCH-CH ₂ H CH ₂ - (OCK-CH ₂ W

³ ' ⁵ I j ψ3 ³ i

ψ i

CK 40GH ₂ CE ₂ ) ~~ · CH-O-CH ₂ CH ₂ -GH ^ OCH-CH ₂ W, CH ^ OCH-CH ₂ W

II ■■■ I ^CH 3 I. ψ3

GH ₂ -O-CH ₂ CH ₂ - ,. GK ₂ ^ H-CH ₂ W, CH ₂ - (OGH-GH ₂ W

' GH ₂ -OGH ₂ GH ₂ -GIi-OGH ₂ CH ₂ -

ι 2 CII-OCH2OH2-

CH * CH _# H)

(j _{H. OOH} ",

CH2 ϊ ^d

■ 1 - ■ CH-OCHpCHp-

COCHoCH ₂ ) -. , ■ - ■■ !. ^^

- ■■■ CH ₂ -OCH ₂ CH ₂ -

Examples of monovalent to hexavalent organic groups that result from bonding an alkylene group with 2 to 4 carbon atoms or a polyether linkage chain derived from a polyalkylene glycol with a Alkylene group with 2 to 4 carbon atoms to one of the Bindings of -OE,> ST,> UH and / or > ÜTR received are, for example, the following:

OH
-CH ₂ CH ₂ OH ₅ -CH ₂ GH ₂ CH-CE ₃ ,

"■■■ - ■ '." ■' .. OH

^h0CrI 2. / ^Cn 2 ~ OH OH OH OH '

■ " _u V ■ \ _rH '- ■" ·. -CHp-GH-CH-CH-CH-CHp-, H- (OGH ₂ GH ₂ W

H- (OCKCHpW

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-s-

HJaC

CK3-.II

CH ₂ CH ₂ -

(CH ₂ CH ₂ O ^ CE ₂ CH ₂ -

(CH ₂ GH ₂ O) -CH ₂ CH ₂ -. . . .

, " ⁴ C ₁₈ H ₃₇ NC

(CH ₂ CII ₂ O) TCH ₂ CH ₂ - » ^iO ■ * ' ^X

Examples of L and Hg in the above formulas are alkyl groups with 1 to 4 carbon atoms such as -CH _x , -C ₀ Hc-, -GH ₀ CH ₀ CH ^ -CHCSSs and -CH ₀ CH ₀ CH ₀ CH ,, where-

j CO ccJ Ott · » <- c- CJ

d hidli i

with the remainders B ... and R £ be the same or different can. -

Examples of B include alkyl groups of 1 to 10
Carbon atoms, for example CH ^ -, C2H, -, CaHg-,
C ^ H ₇ -, and CßH-y and hydroxyalkyl groups with 1 to 3 carbon atoms, for example HOCH «-, HOCHgCH ₂ - and
HIGH ₂ CH ₂ CH ₂ -.

Of the compounds according to the invention corresponding to the above formula, those of the following are general 3 "ormel (1)" especially for use as a surface-active agent for non-aqueous media and as a modifier preferred for polymer compounds:

NtCOCK ₂ CH ₂ O

(1)

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where A is a divalent to hexavalent hydrocarbon group or a divalent to hexavalent organic group with an ether linkage chain, R ₁ and R _{2 are} alkyl groups with 1 to 4 carbon atoms and η is an integer from 2 to 6.

Compounds of the formula (1) ', in which A is a divalent to hexavalent saturated aliphatic hydrocarbons off group with · 1 to 20 carbon atoms, a divalent cycloalkylene group having 5 or 6 carbon atoms or a divalent to hexavalent polyalkylene glycol having an alkylene group of 2 to 4 carbon atoms are even more preferred.

The compounds according to the invention given above are not and are not described in the literature for example, as surfactants, dispersants, chelating agents and modifiers to give Hydrophilicity, softness, antistatic properties, Adhesion, plasticity and other improved properties for or made from polymeric compounds Form objects valuable. For example, as polymer modifiers the compounds according to the invention are added in small amounts to polyvinyl chloride pastes. The obtained compositions maintain low viscosity for long periods of time and have superior workability and deliver products of superior properties. The amount of the compound to be added according to of the invention is 0.1 to about 20 weight percent based on the weight of the vinyl chloride resin. Since the Compounds according to the invention act as superior dispersants in non-aqueous media, they are as colorants dispersant in dyeing using water-insoluble compounds, as a sludge dispersant Their addition to lubricating oils and as a dispersant for

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! Dyes and pigments for coloring synthetic resins valuable. The amount to be used according to the invention Compound when used as a dispersant is, for example, about 1 to about 5 wt .- $ for dyes, about 0.1 to 5 wt .- ^ for lubricating oils and about 0.01 to about 8 wt .- ^ for synthetic resins.

Furthermore, the compounds according to the invention are useful as surface active agents. For example be use them as surfactants for the preparation of non-aqueous dispersions when dispersing a Monomers containing a polar group and an emulsifier for preparing an o / o type emulsion in one Hydrocarbon used as a solvent. Usually can in this application the compounds according to the invention in amounts of about 0.01 to about 5 wt .- ^, based on the dispersing medium. Many compounds according to the invention are with water miscible and these water-miscible compounds can also be used as surface-active agents in aqueous systems can be used. For example, the compounds according to the invention show excellent effects when the particles a carbonaceous substance such as soot, carbon fibers, activated carbon or flake carbon is stable in water be dispersed. For such use, the compounds according to the invention can be used in amounts of about 0.05 to about 5 wt .- ^, based on water, can be used.

The compounds according to the invention are also useful as dispersants for use in manufacture of paper or non-woven cloths by the letting method by dispersing fibers or paper pulp made up of synthetic fibers. The amount of Connections in this application is for example

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about 0.01 to about 0.1% by weight, based on water.

Furthermore, the compounds according to the invention can be used where their solving power is exploited will. As indicated above, the compounds according to the invention are in a wide variety of solvents with an N, N-dialkylamide group such as the super-solvents soluble and have at the same time the ability to dissolve a wide range of substances. Therefore they can be used as staining media for the Printing and immersion staining can be used. In such an application, the amount is, for example 100 to 1000% by weight, based on the dye used.

Since the compounds according to the invention compatibility with a wide variety of polymers, they can easily be processed into masses together with the polymers and can thus be used as modifiers to improve softness, hydrophilicity, antistatic Properties, surface adhesion and other properties are processed. Since the connections continue according to the invention have the ability to absorb ultraviolet rays, they can be used as modifiers can be used taking advantage of this property. The amount in this usage is, for example, about 0.001 to about 10 percent by weight, based on the weight of the Polymers. The compounds according to the invention can also be used as chelating agents or metal ion trapping agents because the ΐΓ, Ν-dialkyl-substituted amide group contained in the compounds according to the invention possesses the ability to bond with metal ions .. The The amount for this purpose corresponds to the amount of metal to be treated or is slightly larger.

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The compounds of the general formula (1) according to the invention can by an addition reaction of a Compound of formula (2)

H _2-p ) _m (2)

where A is a group from the class τοη monovalent to hexavalent hydrocarbon groups, monovalent to hexavalent organic groups with an ether bond chain and monovalent to hexavalent organic groups which, due to the bond of an alkylene group or a polyether bond chain to a bond of -OH, -> H ",> NH and> TR, in which R represents an alkyl group, B hydrogen atoms, alkyl groups and hydroxyalkyl groups, m the numbers 0, 1 or 2, η the numbers 2 to 6, if m is 0 and 0 is 1 or 2 , if m has the value 1, and 0, if m has the value 2, and ρ denotes the numbers O or 1,
and a ΪΤ, ΪΓ-dialkyl acrylamide of the formula

CH ₉ = CHCOIT ^ ^Ί (3)

-R ₂

wherein R ₁ and R _{2 are} alkyl groups having 1 to 4 carbon atoms, τ
getting produced.

The compounds of the formula (1) 'can by an addition reaction of the two hydroxyl end groups Alkane polyol or a polyalkylene glycol corresponding to the formula (2)

A (OH) _n ■ (2) '

wherein A is a divalent to hexavalent hydrocarbon group or a divalent to hexavalent organic group with an ether bond chain and η a

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an integer from 2 to 6, and one F, N-dialky! acrylamides of the formula

f ₉ HC] J ^ ^Ί (3)

■■ · ■ - ^R 2

where R ₁ and R _{2 are} an alkyl group having 1 to 4 carbon atoms ■ are prepared. ..

The compounds of the formula (2) include a large number of compounds which contain a hydroxyl group and / or an amine hydrogen atom, for example alkane, alkene or alkynediols, diols of low molecular weight such as dihydroxyalkyl substituted benzenes or cyclohexanedol, polyalkylene glycols, polyhydric alcohols with at least three functional groups, adducts between these compounds and alkylene oxides, primary amines, secondary amines, mono-, di- or trialkanolamines, N-alkyl-substituted (mono- or di-) alkanolamines, N-alkyl- «substituted (mono- or Di -) - alkanolamines, various alkanolamines and adducts between these compounds and alkylene oxides. Specific examples of such compounds include polyethylene glycols of the formula HO (CH ₂ CH ₂ O) ^ H, where f is an integer of at least 2, preferably an integer from 2 to 500, 1,2-propylene glycol, 1,3-propylene glycol. and polypropylene glycols of the general formula

■ CH,

t ■>

HO (CHCHpO) H

where g is an integer of at least 1, preferably is an integer from 1 to 100,

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Polyether diols such as random copolymers or block copolymers of ethylene oxide and propylene oxide, tetrahydrofuran, its copolymers or block copolymers of formaldehyde and ethylene oxide, saturated or unsaturated hydrocarbon diols having 4 to 20 carbon atoms such as 1,2-butanediol, 1,3-butanediol, cis and trans-2-butene-1,4-diol, 2-batane-1,4-diol, 1,4-butanediol, 2,3-butanediol, 2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-honanediol, 1,10-decanediol, 2,4-heptanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2,2-dimethyl propane-1,3-diol, 2-methyl-2,2-n-propyl-1,3-propanediol, 2-methyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, 2-methyl-1,5-pentanediol, 2,5-dimethy1-3-hexyl-2,5-diol, 2-methyl-1,4-batanediol, 3-methyl-1,4-butanediol, 3,6-dimethyl-4-octane-3,6-diol, 3-methyl-1,5-pentanediol, 2,5 ~ methyl-2,5-hexanediol, 2,3-dimethyl-1,4- butanediol, 2-methyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol and 2-methyl-1,6-hexanediol.

Other examples of compounds of formula (2) include dihydroxyalkyl-substituted benzenes, such as 1,2- or 1,3-cyelopentanediol or 1,2-, 1,3- or 1,4-dihydroxymethylbenzene, cycloalkyl-containing polyhydroxy compounds such as 1,2-, 1,3- or 1,4-cyclohexanediol or 1,2-bis (hydroxymethyl) cyclohexane, Terbindungen with 5 to 6 hydroxyl groups, such as 1,1,1 -trimethylolethane, 1,1,1-trimethylolpropane, Glycerine, 1,2,4-butanetriol, 1,2,3-butanetriol, 2-methy1-1,3,5-pentanetriol, 1,2,6-hexanetriol, erythritol, 1-, d- or dl-erythritol, pentaerythritol, dipentaerythritol, Ribitol, xylitol, arabitol, sorbitol or mannitol, aliphatic primary amines with 1 to 20 carbon atoms such as methylamine, ethylamine, isopropylamine, isobutylamine, pentylaniine, Hexylamine, octylamine, honylamine, decylamine, laurylamine or stearylamine, aliphatic secondary amines with 1 to 10 carbon atoms, such as diethylamine, dibutylamine, or Dihexylajain, aromatic primary amines with 6 to 10 carbon

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fuel atoms, aniline and substituted anilines, such as
Ethylaniline, toluidine, xylidine or 2,4,6-trimethyl- "aniline, aromatic secondary amines with 7 to 12 carbon atoms such as N-substituted anilines, for example N-methylaniline or N-methyltoluidine, alicyclic imines with 3 to 6 carbon atoms, such as trimethyleneimine or hexamethyleneimine, aliphatic diamines with 2 to 8 carbon atoms, such as ethylenediamine, trimethylenediamine,
Pentamethylenediamine, hexamethylenediamine or Oc "tame thy lenediamine, cycloalkylene diamines with 4 to 8 carbon atoms such as piperazine or 1,4-diazacycloheptane, aromatic
Diamines with 6 to 10 carbon atoms such as phenylenediamine or diaminotoluene, diamines of the general type. IOrmel

where r is the number 0, 1 or 2, k is an integer of at least 1, preferably an integer from 1 to 50, and Rj is a hydrogen atom or an alkyl group having 1 mean up to 4 carbon atoms,

N-substituted alkanolamines with 3 to 10 carbon atoms such as U-methylethanolamine, H-ethylethanolamine, N-propylethanolamine, N-phenylethanolamine or N-ethyldiethanolamine, mono-, di- or tr! Alkanolamines with 2 to 12 carbon atoms such as monoethanolamine, diethanolamine , Triethanolamine, n-propanolamine or isopropanolamine,
amine-substituted alkanols with 4 to 10 carbon atoms such as 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) isopropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl -1-propariol or p-aminophenylethyl alcohol and adducts formed between amines and ethylene oxide according to the following formula · -.

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,H

where R is a hydrocarbon group, for example an alkyl group having 1 to 18 carbon atoms or an alkyl-substituted phenyl group and 1 and 1 ^? integers of at least 1, for example 1 to 30, mean.

Examples of H, IT-Dia Iky la cry! Amide of the formula (3) IT, N-dialkylacryamides are used to react with compounds of the formula (2) with 1 to 4 carbon atoms in the alkyl group, such as .z.B. ΪΤ, Ν-dimethylaerylamide, F, 3J-diethylacrylamide, IT, N-Diisopy la cry lamid, IT, IT-Di-n-propylacry lamid, Π, Ν-Di-n-butyla cry lamid, IT-Me thy 1-H-ät hy I- ■ acrylamide, IT-Me thy 1-H-propyla. cry lamid, H-methyl-N-butyla cry lamid or IT-ithyl-ÜT-pr opy la cry lamid.

The compounds of the formula (1) according to the invention can be prepared by contacting a compound of the formula (2) with a compound of the formula (3) in the presence of a basic catalyst. This addition reaction proceeds at room temperature and heating is not particularly necessary. Usually, however, the reaction is carried out at an elevated temperature. The temperature can (2) and (3) are varied and customary v / else be applied temperatures in the range from room temperature up to about 15O ⁰ C according to the kind of the catalyst and the kinds of the compounds of the formulas. Gewünsehtenfalls temperatures can be also applied below room temperature or above 150 ⁰ C. The reaction time is generally about 1 to about 10 hours. The reaction can be carried out in an inert liquid medium, for example water, ketones such as acetone,

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Methyl ethyl ketone or methyl isobutyl ketone, cyclic Ethers such as tetrahydrofuran or dioxane, aliphatic Ethers such as ethyl ether or diisopropyl ether or aromatic Hydrocarbons such as benzene, loluene or xylene are carried out.

In the process according to the invention, a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomettoyl ether or methy! Hydroquinone can be added in order to inhibit the polymerization of the Ν, Ν-dialky.lacrylamides. The amount of the basic catalyst used in the process according to the invention is generally from about 0.1 to about 5 mol, based on the active hydrogen of the compound corresponding to the formula (2). However, the amount can be appropriately changed according to the reactants used and the reaction temperatures, if an organic compound is used. Formula (2) is reproduced as HO-Y-QH and the N, N-dialky! Acrylamide is reproduced as CH ₂ = GHCONC ^ h, the reaction product obtained from these compounds is generally a mixture of HQ-Y- OCH ₂ CH ₂ CONC] JI (P ₁ )> Y (OeH ₂ CH ₂ CONcIn) (Pg) «and unreacted compounds. Since the above reaction is an equilibrium reaction, the conversion of -OH can be changed by adjusting the molar ratio of CH ₂ = CHCONR ¹ R "to the -OH groups, therefore one mole of CH ₂ = CHCONR ¹ R in the above reaction "is reacted with 1 mol of HO-Y-OH, the conversion of the -OH-G group is about 50 j £ and a mixture of 25 mol $ of the unreacted yerbiadungen, 50 mol-? S p ^ 'and 25 MoI- ^ p ₂ can be obtained. Balls "'2 Mo! _{An' CH 2} = CHCONR ^f R" are used ^ a is' Hauptprodulct ρ «occurs.

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The ΝγϊΓ-dialkylacrylamide of the formula (3) asked one marked resistance to the bases used as the catalyst compared to an N-unsubstituted one Acrylamide and therefore the H, H-dialkyl acrylamide molecules react with the hydroxyl group and / or amino group of an organic compound of the formula (2) in more stable

Examples of suitable basic catalysts which are used in the above substitution are alkali hydroxides, such as lithium hydroxide, barium hydroxide or potassium hydroxide, alkali alkoxides of primary, secondary or tertiary n-, iso- or neo-aliphatic alcohols with 1 to 12 carbon atoms in the alkyl group, such as sodium methoxide, potassium methoxide, sodium ethoxide, sodium propoxide (including n- or iso-substituted products), sodium butoxide (including n- or iso-substituted, secondary or tertiary substituted products) or potassium butoxide (including n- or iso-substituted secondary or tertiary substituted products) Alkali compounds (1- or 2-sodium or potassium derivatives) of polyethylene glycol of the general formula HO- (CH ₂ CH ₂ O) H, where q is an integer from 2 to 60 and between the compounds of the above formula. (2) and alkali metals such as sodium, potassium or lithium, formed mono- or poly-substitution products.

The following examples serve to provide a more detailed explanation the invention.

'. :; . ·· :. . ; . = ■■ - example 1,,

In a 100 ml three-necked flask flushed with nitrogen, ⁷ oy552 g of Katricto were dissolved in 93 g of ethylene glycol at low temperature, and 300 g of N, IT-

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-19 - ■

methyl acrylamide and the mixture was stirred at 5O ⁰ C for 4 hours to effect the reaction. After the reaction, the reaction solution was neutralized with glacial acetic acid, and after further adding 200 g of benzene, the mixture was allowed to stand overnight. The obtained sodium acetate was filtered off, and the benzene solution containing the reaction product was heated under reduced pressure to distill off benzene and unreacted matter, and the reaction product was withdrawn. The reaction product weighed 367 g. The infrared analysis (abbreviated IR) and the nuclear magnetic resonance spectrum (abbreviated KMR) showed that N, N-dimethyl acrylamide was linked to the two hydroxyl groups of ethylene glycol by addition of the Michael type without cleavage of the amide bond. The product had an index of refraction A ₁ J ( ^{.25 0} Q) J of 1.4797. The values of the elemental analysis were as follows: C 54 »98 #, H 9.25 $, N 10.49 % and O 25.28 #,.

Example 2

In a nitrogen flushed 500 ml three-necked flask were dissolved in 75.1 g Triathylenglykol 0.260 g of metallic sodium, and then, 100 g of N, N-dimethylacrylamide, and the mixture was stirred for 4 »5 hours to effect the reaction at 52 ⁰ C. After the reaction, the reaction mixture was neutralized with acetic acid, and then after adding 100 g of benzene, it was allowed to stand overnight. The obtained sodium acetate was filtered off, and the benzene solution containing the reaction product was heated under reduced pressure to distill off benzene and unreacted matter, and the reaction product was withdrawn. The reaction product weighed 158 g. Its IR and BMR spectrum showed that N, N-dimethyl-. acrylamide with the two hydroxyl groups of the triethylene

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glycol linked by an addition of the Michael type was without causing side reactions such as cleavage of the amide group.

The reaction product had a refractive index / pj (25 ° C) _7 of 1.4783. The values of the elementary analysis were as follows: C 54.85 , H 9.22 £, N 7.88 fr and 0.28.05. '

Comparative example 1

Example 2 was repeated with the exception that 71.6 g of acrylamide instead of 100 g of N ", Η-dimethyl acrylamide in Example 2 were used. The reaction product was neutralized with glacial acetic acid and then was after Addition of 150 g of acetone removed the sodium compound obtained. The reaction mixture was then at reduced Pressure was heated to remove unreacted matter and then the reaction product was withdrawn. His IR and NMR spectrum showed that part of the amide bond of the acrylamide linked by Michael-type addition was split.

Example 3

In a 500 ml three-necked flask flushed with nitrogen, 0.115 g of sodium was dissolved in 20 ml of methanol and excess methanol was distilled off under reduced pressure. Then, 100 g of medium molecular weight polyethylene glycol was added to the flask to dissolve the sodium methoxide obtained. Then 50.5 g Ν, Ν-dimethylacrylamide were added and the reaction was carried out for 4 hours at 53 ⁰ G. The reaction mixture was neutralized with glacial acetic acid and, after the addition of 100 g of benzene, the reaction mixture was left to stand overnight. The obtained sodium acetate was filtered off, and then the benzene solution containing the reaction product was heated under reduced pressure to obtain benzene.

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zol and unreacted material to be distilled off and the reaction product was withdrawn. The reaction product weighed 128 g. Its IE and NMR spectrum showed that Ν, Ν-diacrylamide with the two hydroxyl groups of the polyethylene glycol was linked by a Michael-type addition without causing cleavage of the amide group.

The reaction product obtained had a refractive index Zn ₁ ) (25 ^ 17 of 1.4739, and the values of elemental analysis were as follows: C $ 56.26, H 9i46 $, N $ 4.60, 0 29.68 fo.

Example 4

In a 500 ml three-necked flask flushed with nitrogen, 0.533 g of sodium were dissolved in 118.2 g of 3-methylpentane-1,5-diol and, after the addition of 200 g of N, N-dimethyl acrylamide, the mixture became at 55 ^° C. to bring about the reaction. After the reaction, glacial acetic acid was added to neutralize the reaction mixture, and after further adding 200 g of benzene, the mixture was allowed to stand over-fold. The obtained sodium acetate was filtered off, and the benzene solution containing the reaction product was heated under reduced pressure to distill off benzene and unreacted matter, and the reaction product was withdrawn. The reaction product weighed 281 g. Its IR and NMR spectrum showed that N, N-dimethyl acrylamide linked to the two hydroxyl groups of 3-methylpentane-1,5-diol by a Michael-type addition without causing side reactions such as cleavage of the amide bond was. ■ - '"""■■. ·

The product had a refractive index ^ n ^ (25 ° C) _7 of 1.4778, and the elemental analysis values were as follows: G 60.78 56, "H 10.20 ^, N 8.60 #, 0 20, 42 fo. -

409882/1201

7Similar example 2

Example 4- was repeated except that 143 grams of acrylamide was used instead of 200 grams of FjF-dimethylacrylamide were used. The reaction product was peeled off in the same manner as in Comparative Example 1. Its IR and NMR spectrum showed that a part the amide bond of the acrylamide linked in a Michael-type addition was cleaved.

Example 5

In a 1000 ml three-necked flask flushed with nitrogen, 1.23 g of sodium were dissolved in 92.1 g of glycerol and then, after adding 495 g of N, N-dimethylacrylamide, the mixture was reacted ^{at 65 ° C. for 4 hours.} Then the reaction mixture was neutralized by adding one equivalent of acetic acid and, after further adding 200 g of benzene, the mixture was left to stand for 2 days. The formed sodium acetate was filtered off, and the reaction mixture was heated under reduced pressure to distill off benzene and unreacted matter, and the reaction product was withdrawn.

The reaction product weighed 370 g and its IR and NMR spectrum showed that'N, N-Dime thy! acrylamide with the three Hydroxyl groups of glycerin by Michael-type addition without causing side reactions such as the cleavage of the amide bond was linked.

The product had a refractive index / n- ^ (25 ° C) 7 of 1.4908, and the elemental analysis values were as follows: C 55.09 #, H 9.06 £, N 10.55 "#, 0.25 , 30 #.

409382/1201

Comparative Free Example 3 ,

Example 5 was repeated except that 355 g of acrylamide instead of 495 g of Ν, Ν-dimethylacrylamide were used. The reaction product was in the peeled off in the same manner as in Comparative Example 1. The IR and NMR spectrum of this reaction product showed that part of the amide bond. of the acrylamide, which by a Michael-type addition was linked, was split. ;

Example 6

In a 500 ml three-necked flask flushed with nitrogen, 0.345 g of sodium was dissolved in a mixture of 67 »1 g of 3-methylpentane-i, 3,5-triol and 5 g of methanol. After removal of methanol were 248 g, Ν, ΪΓ-dimethylacrylamide added and the reaction was carried out for 67 hours at ⁰ C. Then, a Äquivale. t acetic acid was added to neutralize the reaction mixture and, after a further addition of 100 g of benzene, the mixture was left to stand overnight. The obtained sodium acetate was filtered off, and the mixture was heated under reduced pressure to distill off benzene and unreacted matter, and the reaction product was withdrawn. The reaction product weighed 195 g and its IR and NMR spectrum showed that Ν, Ν-dimethylacrylamide with the three hydroxyl groups of 3-methylpentane-T, 3,5-triol by addition of the Michael type without causing side reactions such as the Cleavage of the amide group was linked.

The reaction product had a refractive index / ήρ (25 ⁰ C) J of 1.4892, and the values of elemental analysis were as follows: C 58.30 %, H 9.60 $, N 9.53 ^, 0 22.57 % .

A09882 / 1201

Example 7

Example 2 was repeated with the exception that 128 g of H ", IT-diethylacrylamide instead of 100 g of H, H-dimethylacrylamide were used. The reaction product was withdrawn in the same manner as in Example 2. The IR and NMR spectrum of the product showed that H ", ΪΤ-diethylacrylamide with the two hydroxyl groups of triethylene glycol by an addition of the Michael type without Induction of side reactions, such as, for example Cleavage of the amide bond.

The elemental analysis values of this product were as follows: C 58.96 #, H 9.90 56, IT $ 6.73, 0 24.41 fo.

Example 8

Example 1 was repeated with the exception that 313 g of N, N-diisopropylacrylamide instead of 200 g of IT, IT-dimethylacrylamide were used. The reaction product was withdrawn in the same manner as in Example 8-. Its IR and NMR spectrum showed that ΪΤ, ΪΤ-Diisopropylacrylamid with the two hydroxyl groups of ethylene glycol by addition of the Michael type without induction of side reactions, such as the cleavage of the Amide bond.

The elemental analysis values of this product were as follows: C 64.05 #, H 10.76 #, IT 7.40 #, 0 17.79 $

Example 9

Example 2 was repeated with the exception that 1.20 g of potassium ethoxide were added instead of the sodium. The reaction product was withdrawn in the same way as in Example 2. Its IR and NMR spectrum showed that N, F-dimethyl acrylamide with the two hydroxyl groups of triethylene glycol by a Michael type addition

409882/120 1

without causing side reactions such as for example. wise the cleavage of the amide bond was linked.

This reaction product had a refractive index / nQ (25 ° Ci7 v ° ⁿ 1.4780, and the values of elemental analysis were as follows: C 54.90 #, H 9.23 $, N 7.93 0, .0 27.94 1>.

Example 10

In a 300 ml three-necked flask flushed with nitrogen, 0.100 g of sodium were dissolved in 20 ml of methanol. After removal of excess methanol, the obtained sodium methoxide in 120 g of polypropylene glycol with a-average molecular weight of 1000 was dissolved, and then were 29,7'g N, N-Dimethy added acrylamide! And the reaction was carried out for 4 hours at 75 ⁰ C. Then the mixture was neutralized by adding one equivalent of acetic acid and, after adding 80 g of benzene, the mixture was allowed to stand overnight. The sodium compound was filtered off and the mixture was heated under reduced pressure to distill off benzene and unreacted matter, and the reaction product was withdrawn. The reaction product weighed 132 g and its IR and NMR spectrum showed that Ν, Ν-dimethylacrylamide was linked by a Michael-type addition to the two hydroxyl groups of the polypropylene glycol without causing side reactions such as the cleavage of the amide group.

This product had a refractive index / n ^ (25 ⁰ C17 of 1.4562, and the elemental analysis values were as follows: 0 60.88 fo _t H 10.22 $, N 2.20 5δ, Ο 26.70 ^,

409882/1 2 0 1

Example 11

A reactor equipped with a thermometer, a stirrer and a reflux condenser 500 ml three-necked flask was purged with nitrogen and then a Methanollös was ung that 0,54- g Hatriummethoxid enthie It, ngebracht egg. Methanol was distilled off under reduced pressure and 52.6 g of diethanolamine were added to the solution of sodium methoxide. 198 g of H, N-dimethylacrylamide were then added and the reaction was carried out ^{at 65 ° C. for 4 hours.} The reaction mixture was then neutralized by adding one equivalent of glacial acetic acid and, after adding 150 g of benzene, the mixture was left to stand overnight. The sodium acetate obtained was filtered off and the benzene solution containing the reaction product was heated under reduced pressure in order to distill off benzene and unreacted material and the reaction product was drawn off. The reaction product weighed 185 g and its IR and HMR spectrum showed that Η, Ν-dimethacrylamide linked to the two hydroxyl groups and an amine hydrogen of diethanolamine by a Michael-type addition without causing any lifting reactions, such as the cleavage of the amide group and the reaction product had the structure represented by the following formula:

CH ₃

JJ (CB ₂ CH ₂ OCh ₂ CH ₂ CH ') 2

CH ₃ 0 0 CH ₃

The product had a refractive index / n- ^ (25 ° C) _7 of 1.4972 and the elemental analysis values were as follows: C 56.52 #, H 9.47 #, H 13.92 %, 0 20.09 #.

A09882 / 1201

Example 12

In a 500 ml three-necked flask of the same type as in Example 11, flushed with nitrogen, 0.54 g of sodium methoxide were dissolved in 30.6 g of monoethanolamine and then 192 g of N, N-dimethyl acrylamide were added and the reaction was continued for 3 Hours and 50 minutes at 65 ⁰ C carried out. The sodium acetate obtained was filtered off and the reaction product; benzene solution containing was heated under reduced pressure to distill off benzene and unreacted matter, and the reaction product was withdrawn. The reaction product weighed 160 g and its IR and NMR spectrum showed that Ν, Ν-dimethylacrylamide was linked to one hydroxyl group and two amine hydrogen atoms of monoethanolamine by addition of the Michael type Without causing side reactions, such as the cleavage of the amide group, and the reaction product had a structure according to the following formula:

NCCHgCH ₂ ) ₂ NCHgCHgOCHgCH ₂ CN

δ δ

This product had a refractive index / n ^ (25 ° C) _7 and the values of elementary analysis were as follows: C -56.81% H 9.52 ^, N 15.65 f _r 0 18.02?.

Example 15

In a 500 ml three-necked flask of the same structure as in Example 11, flushed with nitrogen, 0.54 g of sodium methoxide were dissolved in 74.5 g of triethanolamine. Then 193 g of Ν, Ν-dimethylacrylamide were added and die'Rgaktiön was carried out for 4 hours at 65 ⁹ C

409882/1201

leads. Then the reaction mixture was neutralized by adding one equivalent of glacial acetic acid and after addition of 150 g of benzene, the reaction mixture was left to stand overnight. The obtained sodium acetate was was filtered off and the benzene solution containing the reaction product was heated under reduced pressure to Distilling off benzene and the unreacted material and withdrawing the reaction product. That Reaction product weighed 199 g and its IR and BMR spectrum showed that Ν, Ν-Diiaethylaerylamid with the three Hydroxyl groups of triethanolamine through an addition of the Michael type without causing side reactions, such as the cleavage of the amide group, and the reaction product had that by the following Structure shown formula:

The reaction product had a refractive index £ ä.j. (25 ^c C) _7 of 1.4943 and the values of elemental analysis were as
follows: C 56.42 $>, H 9.45? 6 _f N 12.45 #, .0 21.68? S.

Example 14

99 g (1 mol) of Ν, Ν-dimethylacrylamide were placed in a 300 ml three-necked flask flushed with nitrogen and then a 30% by weight aqueous solution containing 31 g (1 mol) of methylamine was slowly added. The mixture was stirred at room temperature for 4 hours.
The unreacted matter and water were distilled off under reduced pressure, and then the reaction product was withdrawn. The weight of the reaction product was 116 g.

409882/1201

The IR and NMR spectrum of the reaction product showed that N, IT-dimethylaerylamide was linked by addition of the Michael type without causing love reactions, such as the cleavage of the amide bond, and the reaction product had the following structure: CH ₅ NHCH ₂ CH ₂ CON (CH ₅ O ₂ ..

The elemental analysis values of the product were as follows: C 57.60 / a, H 10 * 08 #, N 18.21 #, * 0 14.11 %.

Example 15

In a 300 ml three-necked flask flushed with nitrogen, 127 g (1 mol) of υ, ϊΓ-diethylacrylamide, which contained 300 ppm of hydroquinone monomethyl ether, were baked and a 30% by weight aqueous solution containing 45 g (1 mol) Dimethylamine was slowly added dropwise. The mixture was ^{stirred for 3 hours at 40 0} C and the unreacted material and water were distilled off under reduced pressure and the reaction product was drawn off. The reaction product weighed 141 g and its IR and NMR spectrum showed that N, N-diacrylamide was linked by addition of the Michael type without causing secondary reactions, such as, for example, the cleavage of the amide bond, and that the reaction product possessed the Structure according to the following formula: (CH ^ irCH ^ Hg (C ₂ H ₅ ) ₂ .

Elemental analysis values of the product were as follows: C 62.79%, H 11.72 56, H ^- $ 16.20, 0.29 #.

Example 16 .

In a replaced with nitrogen, 500 ml three-necked flask, 61.1 g (t mol) of monoethanolamine and 198 g (2MoI) N, N-Diinethylacrylainid introduced and the mixture was stirred for 4 hours at 55 ⁰ C. The mixture was heated under reduced pressure to remove unreacted JIa-

40988 2/1201

material to be distilled off and the reaction product was drawn off. The reaction product weighed 230 g and its IR and MR spectrum showed that H ", K-dimethyl acrylamide was linked by a Michael addition without causing lifting reactions such as the cleavage of the amide bond, and the reaction product had the following structure:

HIGH ₉ CH ₉ If (CH ₉ CH ₉ COIr

The product had a refractive index / ü- ^ of 1.5027, and the values of elemental analysis were as follows: C 55.58 #, · Η 9.71 $, H 16.15 #, 0 18.56 $>.

Example 17

In a 300 ml three-necked flask flushed with nitrogen, 52.6 g (0.5 mol) of diethanolara and 49.5 g (0.5 mol) of ir, F-DiiEethylacrylan} id were placed and the mixture was at 65 ⁰ C for 4 Stirred for hours. Then, the reaction mixture was heated under reduced pressure to distill off the unreacted material, and the reaction product was withdrawn. The reaction product weighed 91 g 'and its IR and HMR spectrum showed that f-dimethyl acrylamide was linked by Michael addition without causing lifting reactions such as cleavage of the amide bond, and the reaction product had the following Structure:

The product had a refractive index of 1.4987 ^ and the values of Eleisentaranalyse were as follows: C 52.93 # £ H 9.85, H "£ 13.60, 0 23.62 #.

409882/1201

Example 18

58 g (0.5 mol) of hexamethylenediamine and -297 g (3 mol) of H, N-dimethyl acrylamide were placed in a 500 ml three-necked flask flushed with nitrogen, and the mixture was ^{stirred at 50 °} C. for 8 hours . Then, the reaction mixture was heated under reduced pressure to distill off the unreacted matter, and the reaction product was withdrawn. The reaction product weighed 231 g, and its IR and CMR spectrum showed that N, IT-dimethylenediamine was linked with hexamethylenediamine by Michael addition without causing side reactions such as amide bond cleavage, and the reaction product had the following structure :

CH,. '. ■ -' '^ CH,

* - * - Il V,

0. 0

The elemental analysis values of the product were as follows: C 60.84 Jt, H 10.23 Jt, IT 16.45 #, 0 12.48-56.

Comparison example 4

Example 15 was repeated with the exception that 71.1 g (1 mole) of acrylamide instead of 99 g (1 mole) of N, N-dimethylacrylamide were used. The IR and EMR spectrum of the reaction product showed that part of the amide bond of the acrylamide linked by Michael addition was split.

Comparison example 5

Example 16 was repeated except that 71.1 g (1 mol) of acrylamide instead of 127 g (1 mol) of IT, IT diethylacrylamide were used. The IR and IIMR spectrum of the product showed that part of the amide bond of the acrylamide linked by Michael addition

409882/1201

ten was.

Example 19

The respondents shown in Table I. were obtained by any of the following reaction methods (a) "to (d) to give the values shown in Table I implemented the reproduced compounds.

Implementation methods

(a) As in Example 1, a small amount of metallic sodium was added to the reaction system Formation of sodium alcoholate was added and the reaction was carried out using sodium alcoholate as a catalyst.

(b) As in Example 3, a small amount of E sodium methylate was added to the reaction system and the reaction was carried out using it as a catalyst. .

(c) As in Example 15, an aqueous solution of an amine with a Viny! compound of the formula

implemented in the absence of a catalyst.

₂ (^

(d) As in Example 17, an amine compound was mixed with a vinyl compound of the formula

implemented in the absence of a catalyst without special addition of YJasser.

409882/1201

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409882/1201

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409882/1201

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409882/1201

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4098827 1201

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409882/1201

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409882/1201

ORIGINAL INSPECTED

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409882/1201

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409882/1201

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409882/1201

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409882/1201

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409882/1201

ORiGiNAL INSPECTED

Table I - (B) - continued

ο to co co to

ro ο

119 C ₈ K ₁₇ , CqH ₁₇ O 1 1 CH ₃ CE ₃ . d (C ₀ H ₁₇ ) SICKoCHoCOIK ^ IR
MB.
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'. ι HOCHOCH ₂ '-, H 0 1 1 CK ₃ CII ₃ d 11'XI-I ₂ CH ₂ II-ICH ₂ CKoCOrK '^' ³ ti 122 HOCIIoCII ₂ HOCHOCH ₂ 0 1 1 CH ₃ OH ₃ d (HIGH ₂ CH ₂ ) o ^ CHoCIIgCOiX ⁰¹ ^ ■ Il

4> GJ O CD CD 00

Example 20

The compound of the present invention was added to a polyvinyl chloride paste to make the changes to determine the viscosity and the changes in viscosity over time and using this Paste composition, a fabric was dip coated, to make a waterproof tent sheet.

The polyvinyl chloride paste used for dip coating was prepared according to the recipe shown in Table II, and at that time a predetermined amount of each of the compounds shown in Table III was added. The mass was kneaded using a three-roll paint mill. Changes in viscosity and changes in viscosity with time according to changes in the type and amount of the compound of the invention are shown in Tables IV to VI. The viscosity of the paste composition was measured using a B-type viscometer (type BE ₁ a product of Tokyo Keiki Eabushiki Kaisha) (No. 4 rotor, number of revolutions 30 rpm). The measurement took place at a constant temperature of 25 ^° C.

The polyvinyl paste composition thus obtained was applied to each of various of polyvinyl alcohol or Polyester fibers made up of tent sheets by dip coating upset. For comparison, a common paste composition was used that was similar to the bulk of the recipe given in Table II, with the exception that 8 parts of trichlorethylene was used instead of compound according to the invention were added.

The polyvinyl alcohol-based cloth used was a smooth cloth with a unit weight of 305 g / m 2 and the polyester-based cloth used was a smooth one

403882/1201

Cloth with a unit weight of 286 g / m. The cloth was desized and cleaned using the usual methods and passed through hot rolling in a moist heat to finish the surface to a smooth state, to make a test ground cloth.

A test base cloth, which was cut to a size of 50 × 50 cm, was immersed in a bath of the paste composition and squeezed off by a mangle which had two rubber rollers to a resin absorption of 70% by weight. It was held vertically in a hot air dryer and preheated at 100 ⁰ C for 5 minutes and then cured at 180 ⁰ C for 3 minutes.

The waterproof tent sheets obtained were examined for water resistance and adhesive property. As waterproof became the initial resistance to water pressure after treatment, the resistance to Water pressure after flexing and the degree of leakage tested. The resistance to water pressure was using a conventional water pressure resistance tester. The degree of leakage was determined by the degree of leakage for long periods of time rated at low water pressure (around 50 mm HpO). The interfacial bonding strength between the polyvinyl chloride resin layer and the base blanket was tested using an Instron tester after superimposing two treated cloths and bending measured by a high frequency welder. The flexural strength was the peel strength of the binding section. The results are given in Table VII.

409882/1201

Table II Compounds to be mixed

Polyvinyl chloride resin paste (Geon 121, a product of Nippon Zeon Co., Ltd.)

Dioctyl phthalate

Calcium carbonate

(Sunlight Fr. 700,. A product of the

Takehara Kagaku Kogyo Kabushiki Kaisha)

Titanium dioxide pigment

(KA-30, a product of Nippon Titanium

Eogyo Eabushiki Kaisha) Ba-Zn type stabilizer

(a product of the Sakai Eagaku Kogyo

Kabushiki Eaisha)

compound according to the invention

amounts

Parts 80 parts

20 parts 10 parts

2 parts

specified 'amount

Table III

sample

chemical formula

^GE 3 \ 1

H ₂ (OCH ₂ CH ₂ ) ₃ OCH ₂ CH ₂ C Ii < _c ^

C ₂ H ₅ "Y ^e J $

C Hc ^{> Νΰ0Η} 2 ° ^Η 2 (OCH ₂ CH) ₈ OCiI ₂ OK ₂ CIf <

409882/1201

Table IV

Viscosity of the polyvinyl chloride paste containing compound A

Viscosities of the paste (poisen)

sample
No. - Amount of
link
A (PHR) immediate
cash after
Manuf
lung 1 day
later 2 days
later 5 days
later 10 days
later 1 O 103 110 128 175 210 2 0.7 63 76 76 78 80. 3 1.0 58 56 57 58 60 4th 2.0 50 53 51 53 55 5 2.9 52 56 53 51 55 Table V.

Viscosity of the polyvinyl chloride paste containing compound B

Viscosities of the paste (poisen)

sample
No. Amount of
link
B (PHR) immediate
cash after
Manuf
lung 1 day
later 2 days
later 5 days
later 10 days
later 1 0 107 115 130 168 205 2 0.5 56 59 63 66 70 3 1.0 49 53 53 55 • 52 4th 2.0 45 44 44 46 - 47 5 3.0 46 44 47 49 55

40.98-82 / 1201

Viscosity of the compound C according to the invention containing Polyvinyl chloride paste

Viscosities of the paste (poisen)

sample
ITr. · Amount of
link
C (PHR) immediate
cash after
Manuf
lung 1 day
later 2 days
later 5 days
later 10 days
later 1 O 110 115 128 175 213 2 0.5 72 67 65 68 70 3 1.0 44 41 40 43 43 4th 1.5 35 37 37 3S 40 5 2.0 40 38 36 38 40

409882/1201

Table VII

sample
ufr. material
of the basic
cloth water-·
repulsive
send ma
appropriate
Treat
lung according to the invention
link lot
(PHR) water-repellent own
societies Resistant
speed against
over waters
reprint
Flex fatigue
(MnH ₂ O) Extent of
Breakthrough
core
(Days) Release
firm "-
iceit des
composite
those
Part
(kg / 3 cm
Broad) 1 PVA ⁺ no Art 0 Resistant
speed against
over water
reprint
treatment
(ramH ₂ 0) 800 oozed
after 2 days
gen through 5.0 2 PE ⁺ * no - 0 900 750 ti 4.8 - 3 . PYA there - 0 800 > 1500 ' no through
seep wah
rend 7th days 3.9 4th PE Yes mm 0 > 1500 > 1500 Il 3.6 5 PVA ' no - 1.0 > 1,500 H It 6.8 6th PVA no A. 2.0 Il Il Il 6.9 7th PE no A. 1.0 Il Il Il 6.7 8th PE no A. 2.0 Il Il Il 6.9 9 PVA no A. 1.0 ti It Il 7.3 10 . PVA no B. 2.0 Il Il It 7.5 11 PE no B. 1.0 ti Il H 7.0 12th PE no B. 2.0. H Il It 7.1 13th PVA no B. 1.5 Il dd Il 6.5 14th PVA no G 2.5 Il It Il 6.7 15th PE ' no C. 1.5. Il Il It 6.4 16 PE no C. 2.5 Il Il Il 6.5 C. It,

PVA = polyvinyl alcohol,

PE = polyester

From the above results, it can be seen that the polyvinyl chloride paste composition containing the novel compound of the invention has a low viscosity and a very reduced tendency to increase in viscosity with time. The treated using the above paste composition airtight waterproof tent sheet has good waterproofing characteristics without wasserab- 'pointing solubilizing Be-treatment of the base cloth and the adhesion between the resin and the base cloth is also superior.

Example 21

The following four compounds (D, E, P and G) were tested to examine their effects as dispersants. The test consisted of preparing a dispersion system having a fine particle concentration of 1 g / 100 ml and a dispersant concentration of 0.5 g / 100 ml using a 100 ml graduated cylinder, stirring the system by rolling the measuring cylinder 12 times , allowing to stand at 25 ⁰ C and measuring the rate of fall of ITiederschlagsoberfläche. The results are given in Tables VIII to XI. The numbers in the tables show the cylinder graduation of the precipitation surface and 100 shows a good state of dispersion without any noticeable precipitation surface. The blank means a system that does not contain a dispersant.

The following four compounds were used as dispersants.

409882/1201

ο - ο

^D > i)

^CH 3

40 9882/170 1

Table VIII TiO ₂ / Benzolaystem

Time Dispersants D. 100 J ¹ G Blank sample D. E. 91 F. G Blank sample ¥ G Blank sample (H) 100 100 99 95 23 100 100 80 100 100 98 100 99 Precipitation
completed 1 99 99 98 90 Precipitation
completed 100 100 65 95 72 Precipitation
completed 100 97 H 2 98 99 96 81 Il 98 100 21 83 34 Il 99 93 Il 3 95 98 92 63 η 95 99 76 Precipitation "
completed 98 85 Il -4 90 93 95 45 η 86 99 63 96 70 Π VJl 66 40 Precipitation "
completed Table X γ- -Fe ₂ O ^ 18th Table IX Carbon black / methanol systems D. / Trichlorethylene system Dispersants dispersant Time E. 97 1 hour 94 1 day 90 2 days 80 3 days Failure 63
lung be
ends 5 days - Time
(Min.) 1 2 3 VJI 10 ·

409882/1201

Table XI CaCO ^ / oxoctylphthalate system

Time D. - * 87. Dispersants I ¹ G Blank sample (H) 99 74 E. 98 100 71 1 93 45 100 91 99 Precipitation 2 . 95 completed 86 97 dd 3 90 72 93- U 5 ■ 83 40 83 Il 8th 65

409882/1201

Claims (1)

Claims 1. Compound of the formula (D wherein A is a monovalent to hexavalent hydrocarbon group, a monovalent to hexavalent organic Group with an ether linkage chain or a monovalent one to hexavalent organic group resulting from the bond of an alkylene group or a polyether bond chain to one of the bonds of -OH, ■>] ?, > NH or> liH, in which R represents an alkyl group, was obtained, R ... and Rg an alkyl group with 1 to 4 · carbon atoms, B hydrogen Atoms, alkyl groups or hydroxyalkyl groups, m the Numbers 0, 1 or 2, η an integer from 2 to 6 if m represents the number 0, the numbers 0, 1 or 2 if m represents the number 1 and the number 0 if m represents the number 2 represents, and ρ denotes the numbers 0 or 1. ■ 2. Connection according to claim 1, characterized in that that in the formula (1) A is a monovalent to hexavalent saturated aliphatic hydrocarbon group, a monovalent cycloalkyl or divalent cycloalkylene group, a monovalent to hexavalent polyalkylene glycol radical or monovalent to hexavalent organic groups formed by bonding an alkylene group or a polyether linkage chain derived from a PcIyalkyleneglykol with two to four carbon atoms in the alkylene group, to one of the bonds of -OH, ^ IT, XUH or 409882/1201 Where R represents an alkyl group having 1 to 20 carbon atoms, R 1 and R ₂ an alkyl group having 1 to 4 carbon atoms and B hydrogen atoms, alkyl groups having 1 to 10 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms mean. 3. A compound according to claim 2, characterized in that in the formula (1) A is a monovalent to hexavalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent cycloalkyl or divalent cycloalkylene group with 5 or 6 carbon atoms, a monovalent to hexavalent one. Polyalkylene glycol with a content of 2 to 4 carbon atoms in the alkylene group or a monovalent to hexavalent organic group resulting from the bond of an alkylene group having 2 to 4 carbon atoms or one Polyalkylene glycol with 2 to 4 carbon atoms -in the Alkylene group on one of the bonds of -OH, ^ N, > NH or> NR, in which R represents an alkyl group having 1 to 20 carbon atoms, has been obtained. 4. A compound according to claim 1, characterized by the following formula (1) LR2 (D wherein A is a divalent to hexavalent hydrocarbon group or a divalent to hexavalent organic group with an ether bond chain, R ₁ and R are an alkyl group with 1 to 4 carbon atoms and η is an integer from 2 to 6. 409882/1201 5. A compound according to claim 4 »characterized in that that in the formula (1) 'the radical A is a divalent to hexavalent saturated aliphatic hydrocarbon group containing 1 to 20 carbon atoms, a divalent alkylene group containing 5 or 6 carbon atoms or a divalent to hexavalent polyalkylene glycol radical containing 2 to 4 carbon atoms in the alkylene group means. 6. Process for the preparation of a compound of the formula (1) R2 . (D wherein A is a monovalent to hexavalent hydrocarbon group, a monovalent to hexavalent organic group with an ether linkage chain or a monovalent to hexavalent organic group resulting from the bond of an alkylene group or a polyether bond chain to a bond of -OH,} H,> NH or> NR, where R is an alkyl group, R. and R ₂ an alkyl group with 1 to 4 carbon atoms, B hydrogen atoms, alkyl groups or hydroxyalkyl groups, m the numbers 0, 1 or 2, η an integer from 2 to 6, if m has the value 0, a number 0, 1 or 2 if m has the value 1 and a number 0 if m has the fourth 2, and ρ denotes the numbers 0 or 1, characterized in that a compound of the following !Formula Β2. _ρ ) _η (2) 409882/1201 wherein A, B, m, η and ρ are those given above Have meanings and a Ν, ΪΤ-Dialkylacrylamid der formula / R ₁ · CH ₂ = CHGON _VR '(3) wherein R ^ and R _{2 have} the meanings given above, are subjected to an addition reaction. 7 · Process for establishing a · connection'der Formula 1)' "R ₁ wherein A is a divalent to hydrocarbon group or a divalent to hexavalent organic group with an Itherbindungskette, R .. and R _{2 is} an alkyl group with -1 to 4 carbon atoms and η is an integer from 2 to 6, characterized in that a E, IT-Dialky! Acrylamide of the formula (3) wherein L and R _{2 have} the meanings given above, with the two terminal hydroxyl groups of an alkane polyol or polyalkylene glycol of the formula A (OH) _n (2)> wherein η has the meaning given above, is subjected to an addition reaction. 8. Resin composition containing a compound of the formula (D 409882 / -1201 ^Y n. R2 2-p (D wherein A is a monovalent to hexavalent hydrocarbon group, a monovalent to hexavalent organic group with an ether linkage chain or a monovalent to hexavalent organic group which is formed from the bond of an alkylene group or a polyether bond chain to a bond of -OH, ^ fT,> NH or> NR , wherein R represents an alkyl group, R ₁ and R ₂ .an alkyl group with 1 to 4 carbon atoms, B hydrogen atoms, alkyl groups or hydroxyalkyl groups, m the numbers O, 1 or 2, η an integer from 2 to 6, if m is 0, a number 0, 1 or 2 if m is 1, and a number 0 if m is 2, and ρ is 0 or 1 and a vinyl chloride resin. 9. Use of a compound of the formula LR ₂ 1 © (CK ₂ CH ₂ GOi /) \ r-, E wherein A is a monovalent to hexavalent hydrocarbon group, a monovalent to hexavalent organic group with an ither bond chain and a monovalent to hexavalent organic group resulting from the bond of an alkylene group or a polyether bond chain to the bond of -OH,> 1T,> NH or > KR, where R is an alkyl 409882/1201 group, R ₁ and R _{2 are} alkyl groups with 1 to 4 carbon atoms, B are hydrogen atoms, alkyl groups or hydroxyalkyl groups, m is the number O, 1 or 2, η is an integer from 2 to 6, if m is the value Has 0, a number 0, 1 or 2 if m is 1, and a
Number 0, if m has the value 2, and ρ denotes the numbers O or 1, as a surface-active agent. 409882/1201