CA1248271A - Heat cross-linkable polymer compositions and their production process - Google Patents

Heat cross-linkable polymer compositions and their production process

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Publication number
CA1248271A
CA1248271A CA000492410A CA492410A CA1248271A CA 1248271 A CA1248271 A CA 1248271A CA 000492410 A CA000492410 A CA 000492410A CA 492410 A CA492410 A CA 492410A CA 1248271 A CA1248271 A CA 1248271A
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Prior art keywords
cross
binding agent
linking
butadiene
binding
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CA000492410A
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French (fr)
Inventor
Klaus Gorke
Christoph Herrmann
Roland Streck
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Evonik Operations GmbH
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Huels AG
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00Compositions of rubbers containing carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/006Rubber characterised by functional groups, e.g. telechelic diene polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034Materials or components characterised by specific properties
    • C09K2003/1059Heat-curable materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617Polyalkenes

Abstract

ABSTRACT OF THE DISCLOSURE
Heat cross-linkable polymer compositions and their production process The present invention relates to heat cross-linkable masses that consists of a binding agent and conventional addi-tives, additives that catalyse the cold cross-linking being excluded, and a process for producing cold cross-linking masses, such that a binding agent, an effective quantity of one of the additives that catalyst the cold cross-linking, and additional conventional additives are mixed together. The binding agent is a combination of two binding agents that are capable of cross-linking with each other without the addition of a cross-linking agent. These binding agents are a polymer that bears primary and/or a secondary hydroxyl group based on 1,3-butadiene and a polymer based on 1,3-butadiene with side Bernstein acid anhydride groups. The masses according to the present invention can be used for an extremely wide variety of applications.

Description

The present invention relates to a heat cross-linkable ~` n ~~ 4 f~ en~ s~
composition containing a -~T}-~u~ier~ b~e~ functional polymer as a binding agent and a cross-linkiny agent and to a process for the production of the cross-linkable composition.
The compositions may be used for various purposes, for example, as joint sealing compounds, adhesive, putties, fillers and vibration dampers.
Heat cross-linkable polymer compositions and polymer compositions that crosslink when cold, which consist of a 1,3-butadiene-based polymer containing a primary or a secondary hy-droxyl group with a number average molecular weight (Mn) of 500 to 10,000 as a binding agent, a diisocynate, for example, toluylene diisocyanate and diphenylmethane diisocyanate as a cross-linking agent, and conventional additives, are already known.
These compositions known in the art have a disadvantage that the cross-linking agent is not absolutely safe from the point of view of industrial safety, and for this reason particularly extensive precautions must be taken when they are being used.
For this reason there has been made a great effort to '>~ replace the diisocyanate by another cross-linking agent that is safer to use.
As an example, U.S. Patent No. 3,624,014 proposes that the bonding agent be cross-linked by -the tin-II-catalysed inter-esterification of a tetraalkyl silane.
It has also been proposed that a polymer having a ter-minal carboxyl group obtained by the conversion of a 1,3-buta-diene-based polymer with a cyclic dicarboxylic acid anhydride be ~sed as a binding agent and a diepoxide be used as a cross-linking - 1 - ~q agent (German Patentschrift No. 21 ~0 949, German OL-fenlegung-sschrift No. 27 41 453 and U.S. Pa~ent No. 3,897,514; see also German Offenlegungsschrift No. 22 05 209 and German Patentschrift No. 22 57 053).
Finally, heat cross-linkable colymer compositions and polymer compositions that can be cold cross-linked are already known in European Patent No. 49 098~ The compositions consist of a combination of two binding agents, a cross-linking agent that lets the two binding agents cross-link with each other, and usual additives. Here, an example of the first binding agent is an epoxy resin and an example of the second binding agent is poly-butadiene modified by maleic acid anhydride.
Even these last-mentioned compositions have a disadvan-tage that the time needed to complete the cross-linking is rela-tively long.
Therefore the desire has remained that these disadvan-tages of the prior art that have been set out above are elimin-ated.
The present invention provides a cross-Iinkable ~a polymer composition comprising (a) a binding agent which is a combination of (i) 10 to 90 weight ~ based on the combination of a binding agent I which is a functionalized 1,3-butadiene-based polymer having a nu~lber average molecular weight (Mn) of 500 to 10,000 containing a primary or secondary hydroxyl ~roup and which has a hydroxyl value of 5 to 200, and (ii) 90 to 10 weight ~ based on the combination of a binding agent II which is a functionalized 1,3-butadiene-based polymer having a number ~2'~

average molecular weight (Mn) of 500 to lO,000 containing a Bernstein acid anhydride side group and which has an acid value of lO to 300, wherein the base polymer of each of the binding agent I and the binding agent II is a 1,3-butadiene homopolymer or a copolymer of at least 70 weight % of 1,3-butadiene and at most 30 weight % of a monomer copolymerizable with 1,3-butadiene selected from the group consisting of a 1,3-diene other than 1,3-butadiene and an alpha-olefin; the base polymer may have been isomerized, hydrogenated or cyclized and (b) a cross-linking amount of a carboxylic acid esterification catalyst selected from the group consisting of (alkyl)benzenesulfonic acids, paraffin sulfonic acids and organic primary, secondary or tertiary amines which are not acyclized under the cross-linking conditions where the amines are cyclic, provided that triethylamine is excluded, wherein the binding agents and the cross-linking agent are selected such that the binding agents I and II cross-link each other without the addition of a further cross-linking a~ent. The cross-linkable polymer composition may further comprise (c) one or more conventional additives.
Preferred embodiments of the present invention are as follows: the binding agents I and II are in each instance present in a quantity of 20 to 80 weight % based on the combin-ation; the number average molecular weight (Mn) of the polymer that forms the basis of the binding agents I and II is l,000 to 8,000; the hydroxy value of the binding agent I is lO to 150; and the acid value of the binding agent II is 20 to 250.

~;

~The composition may be produced by mixing the ingredients.
The present invention also provides a process for producing a cold cross-linking mass, which comprises mixing the binder composition with an effective amount of a cold cross-linking catalyst.
The present invention Eurther provides a process for producing a cross-linked mass which comprises cross-linking a cross-linkable composition comprising a binding agent which is a combination of 10 to 90 wt.~ of the binding agent I and 90 to 10 wt.~ of the binding agent II, either without or under heating, wherein [A] the cross-linking without heating is performed in the presence of a cross-linking amount of a carboxylic acid esterification catalyst selected from the group consisting of (alkyl)benzenesulfonic acids, paraffin sulfonic acids and organic primary, secondary or tertiary amines which are not acyclized under the cross-linking conditions where the amines are cyclic, provided that triethylamine is excluded, [B] and the binding agents and the carboxylic acid esterification catalyst where needed are selected such that ~a the binding agents I and II cross-link each other without the addition of a further cross-linking agent.

~. ~

The cross-linking principle of the composition according to the present invention lies in the fact that an ~dditi~nal esterification reaction takes place be-tween the primary or secon-dary hydroxyl groups of binding agent I and the Bernstein acid (maleic acid) anhydride groups of binding agent II. When this ta~es place, Bernstein acid semi-ester groups are Formed and these link together the macromolecules that constitute the binding agents. The binding-agent matrix that is so formed has free car-~oxyl groups and optionally free hydroxyl groups or free Bernstein 1~ acid anhydride groups. These functional groups and optionally the functional groups of binding agent I and II can react with suit-able functional groups of the additives and the substrates with which the composition come into contact when used.
The production of the binding agents I and II is basic-ally known.
Binding Agent I

. _ Bamford et al have described the way to radical polymer-isation with 4.4'-azo-bis-(4-cyanopentano7-l) as an initiator (~rans. Farad. Soc. 56 (1960) 932). Radical polymerisation with hydrogen peroxide as the initiator is described in German Offen-legungsschrift No. 23 23 677, U.S. Patent Nos. 3,673,168 and 3,714,110 and British Patent No. 957,788. Anionic polymerisation with di-lithium compounds as the initiator and the conversion of the di-lithium terminated polybutadiene with ethylene oxide during the formation of a di-hydroxyl terminated polybutadiene is described in German Auslegeschrift No. 24 06 092, U.S. Patent No. 3,109,871, and German Offenlegungsschrift No. 30 42 559. The ~ 7a~ b~ f-Q~ 7c ozonolysis of higher-molecular ~ t-~h~e and the reduction of the ozonides so obtained, with the formation of di-hydroxyl terminated polybutadienes is described in JP-PS 9 002-890 and SU-PS 590 314.
The substituted polybutadienes at the ends of the chains are designated as telechelically functionalized polymers.
Polymers with statistical distribution of the hydroxyl groups along the macromolecular longitudinal axis are also known.
The conversion of a semi-ester of a maleinized polybutadienes with an aminoalcohol is described in European Patent No. 87 256. The addition of formaldehyde to a polybutadiene with the formation of hydroxymethyl groups is described in the German patent application under file number P 33 46 714. The polymers having these hydroxy-methyl groups are preferred as binding agent I.
Binding Agent II
As a rule, binding agent II is obtained by the addition of maleic acid anhydride (MSA) to a polymer based on 1,3-butadiene ~see, for example, German Auslegeschrift No. 23 62 534).
In special cases the binding agent II can be obtained by the addition of MSA to a polymer based on 1,3-butadiene that ~0 already has other functional groups, in particular reactive silyl groups, for example, trimethoxysilyl groups. Polymers bearing groups of this kind, based on 1,3-butadiene, can be obtained as set out in German Patentschrift No. 30 2~ ~339.
It is preferred that the binding agents I and LI be functionalized homopolymers of 1,3-butadiene. They can also be functionalized copolymers, the basis of which is formed by at least 7Q weight % of 1,3-butadiene and at most 30 weight ~ of other copolymerizable 1,3-(cyclo)dienes, such as, for example, isoprene and cyclopentadiene, or copolymerisable alpha-olefins, such as, for example, styrene and ethylene.
As a rule, the functionali~ed polymers are obtained by functionlization of the basic polymers. These can be obtained in the already known manner by the anionic polymerisation, in partic-ular with a lithium-organic catalyst, optionally in the presence of a Lewis base, in particular a Lewis base selected from the group consisting of ethers, tertiary amines and mixtures thereof, 1~ as a co-catalyst. It is preferred that they are obtained by the 2iegler polymerisation, in particular with a nickel catalyst.
The additives that catalyze the cold cross-linking of the binding agents I and II with each other are conventional acid esterification catalysts, Eor example, (alkyl)benzene sulfonic acids and paraffin sulfonic acids, and organic nitrogen bases, which in the main are not acylized under the conditions of the cross-linking where they are cyclic. Suitable additives are, in particular, sterically hindered primary and secondary amines, tertiary amines and N-alkylimidazoles. Triethylamine, however, ~(~ is excluded. Compositions that contain additives of this sort cross-link at room or ambient temperatures. Particularly short cross-linking times are achieved if the masses are warmed.
Cross-linking times depend on the reactivity of the hydroxyl groups of binding agent I (primary hydroxyl groups more reactive than secondary hydroxyl groups), on the reaction temper-ature, on the type and quantity of the catalyst used, and on the type and quantities of other additives that are used.

Conventional additives are, for example, those addi-~;

tives, extenders, fillers and modifying components that are capable of reacting.
The additives are, for example, anti-aging agents and agents that provide protection against light, pigments, dyes that are soluble in the mass, adhesive agents, thickeners, flame-retardant additives, smoke-retardants, in some cases, additives that promote combustion. The additives can have groups that are capable of reaction with the anhydride groups of binding agent II
and/or the carboxyl groups of the binding-agent ma-trix. These are bound into the cross-linked mass so that damping and migration losses, as well as efflorescence are avoided.
The extenders are conventional extender oils and softeners. They serve to reduce the viscosity of the masses and render them less costly.
Suitable fillers are, for example, soot, talcum, mica, asbestos, kaolin, other natural and synthetic silicates, quarz meal, sand, precipitated and pyrogenous silicic acid, ground slag, fly ash, cement, gypsum, barium sulfate, powder, platelet or fibre metals and oxides, carbides, nitrides and borides thereof, alumin-um hydroxide, magnesium hydroxide, coarse ground rubber, and syn-thetic polymers, for example, PVC, polyolefins and polystyrene, in the form of fibres, powders or foam.
Under certain circumstances the combination of the fillers with the binding-agent matrix can be greatly improved by the addition of conven-tional adhesive agents, for example, such as those from the group of the organo-functional silanes and titan-ates.

Suitable fillers are also glass fibres, glass micro-balls, and other silicate fillers. These can be coated with silanes that have amino groups or epoxy groups, so that they are capable of reacting with the anhydride groups of the binding agent II and/or the carboxyl groups of the binding-agent matrix.
Cross-linked masses that are extremely tough and tear resistant can be obtained with fillers that are capable of reacting directly with the anhydride groups of the binding-agent snatrix, for example the oxides, hydroxides, basic carbonates and la carbonates of alkaline earth metals and of zinc and the oxide and hydroxide of aluminum. Chalk is especially preferred in this regard.
Organic fillers, the surfaces of which have primary and/or secondary hydroxyl groups, for example, starches, cellulose fibres, cellulose powder, wood meal, ground nut shells, rice husks, cork meal, ground leather, and the like, are capable of reacting directly with the anhydride groups of binding agents I
and II and with the carboxyl groups of the binding-agent matrix.
Fillers of this type are bound into the cross-linked mass and for this reason can contribute greatly to the firmness and elasticity ~of the mass~.
The modifying components that are capable of reaction with the anhydride groups of binding agent II and/or the carboxyl groups of the binding-agent matrix are, for example, as yet unhardened epoxy resins, phenoplasts, aminoplasts, ketone resins, which are optionally hydrogenated, copolymers of maleic acid anhy-dride with alpha-olefins,polyethylene glycol, polypropylene gly-B~

col, polytetramethylene glycol, as well as other materials sub-stances that are usual in the polyurethane area and used as hydroxyl components.
The functionalities of the binding agents I and II are to be so selected that the functionality of the binding agent II
is sufficient for formation of -the binding-agent matrix and the reaction with the fillers, the additives and the modifying compo-nents. A few orientation trials will be sufficient to do this.
As a rule, the ratio of the Bernstein acid anhydride 1~ groups in the binding agent II to the primary and/or secondary hydroxyl groups in the binding agent I for the formation of the binding-agent matrix is approximately 1:1 and corresponding to this the ratio of the product from the acid number and the quan-tity of the binding agent II to the product from the hydroxyl number and the quantity of the binding agent I is approximately The cross-linking density that can be achieved with the masses according to the present invention can be adjusted within wide limits by variation of the hydroxyl and acid numbers, the ` W~J~ ~
molecular-~ and the quantitative proportions of binding agent I
and II,relative to the binding agent combination, and optionally by the type and quantity of the additives, so that hard or soft cross-linked masses with high or low cross-linked densities can be obtained, depending on the intended use of such masses.
Apart from the exemplary applications cited in the introduction hereto, for which the masses according to the present invention are of interest, one can add the following: erasers, g _ screening material to provide protection against elec-tromagnetic and nuclear radiation, noise attenuators, molding masses for cables; masses suitable for the production of sealing gaskets ~0-rings]; solid propellants and solid rocket propellants, in which regard the additives that are used contain ammonium perchlorate as well as other materials that affect combustion, such as aluminum powder, ferrocen- and/or carboran compounds.
The presen~ invention will be explained below on the basis of the examples that follow, wherein parts (T) refer to ~ jq~ ~ei5~t ~1~ parts by ~a`~ and percentages (5) to percentages by ~.
Mn of the functionalized polymers that form the basis of the binding agents I was determined chromatographically by gel permeation. Mn of the base polymers that form the basis of the binding agents II was determined osmometrically by vapour pressure.
The viscosity of the binding agent I and binding agent II was determined at 20C according to DI~I 53 015.
The hydroxyl value (OHV) of binding agent I was determined according to DIN 53 2~0 and the acid number (AV) of binding agent II was de-termined according to DIN 53 ~02.
The gel content of the cross-linked masses was measured indirectly by dissolving a sample in toluol at 20C, separating the undissolved portion by filtration and gravimetric measurement of the dissolved portion.
The Shore hardness A of the cross-linked masses was measured according to DIN 53 505.
The following base polymers form the basis of binding agents II:

.,L2~

Table I

_ Microstructure*
Mn 1,4-cis 1,4-trans Vinyl Polybutadiene A ca. 1 700 ca. 72 % 27 % 1 %
Polybutadiene B ca. 2 750 ca. 80 % 19 ~ 1 %

Notes: Polybutadiene C and polybutadiene A, are obtained by con-version with vinyltrimethoxysilane during formation oE trimethoxy-sil~l groups (2.5~ Si, relative to the conversion product) according to German Patentschri-Et No. 30 28 839.
*recurring units that are obtained by 1,4-cis, 1,4-trans, and 1,2 polymerisation of 1,3-butadiene and measured by IR analysis.
Production of binding Agents IA to IF
1~ The binding agents IA to ID were obtained by conversion from polybutadiene oils with different Mn, the microstructures of which corresponds to the microstructures of the polybutadiene oil A in Table 1, with varying quantities of paraformaldehyde in the presence of 0,5~ 2.2-methylene-bis-(4-methyl-6-tertiary butyl phenol), relative to the polybutadiene oil, as described in German patent application P 33 46 714.5.
The binding agent IE was obtained as is described in EP-OS 87 526.
The binding agent IF is a commercially available telechelically functionalized polybutadiene.

Table 2 ¦ Binding AgentMn OHV [mg KOH/g] Viscosity [mPa s]

IE _ 137 IF _ 42 5 000*

~ measured at 30C
Production of Binding Agents IIA to IIC
The binding agents IIA to IIC were obtained by conver-sion of the polybutadiene A or B or C of Table 1 with 7.5% MSA in the presence of 0.05% N-isopropyl-N'-phenyl-p-phenylenediamine, in each instance relative to the mixture of polybutadiene and MSA, ~190C, 2 h).
Table 3 Binding Agent AV [mg KOH/g~ Viscosity [mPa~s]

The production of heat cross-linkable, filler-free masses and cross-linking such masses (Examples 1 to 8) In each instance 100 g of one of the binding agents I

was mixed with a quantity (cited in the following Table 4) of a binding agent I, this being done at room temperature. The masses f~

so ob~ained were cross-lin~ed by being heated to 100C for two hours. The cross-linked masses were slightly coloured, clear, and free of bubbles.

~L2~3ff~

O ~ ~ u~ r o ~
~n X

C
C~
0 0~
C) ~_1 U') ~ ~ 0 ~ ~ ~9 0 ~ I` r~ 0 0 t- ~

H H
~ C

~ C
~ ~ ~ ~ O O O ~ O ~
3 c ~ ~ N ,~
~0 O
O $
_ _ _ ~H
C
. ~ r~ I~ 0 0 ~ ~ ~
c a) ,_ ~1 ~ ~9 ~) ~ u~ ~ 0 '~ ~ ~

~ C
a~ o 1~ H 1--1 H H H H H H
H H H H H H H H
~1 I
~,~ ~
~ ~ H H H H H H H H
C o ~ ~l ~
~o E~

- 14 ~

3 ~

The production of cold cross-linking, filler-free masses and cross-linking such masses (Examples 9 - 12) In each instance, 100 g of binding agent IIB were mixed into the quantities shown in the following Table 5 of one of the binding agents I. Then 1% N-methylimidazole, relative ~o the binding agent combination, were mixed in at room temperature. In the case of Example 12, an additional ]5 g of a paraffin oil were also mixed in. The masses obtained according to Examples 9, 11 and 12 were heated to 45C for 15 mins. The mass obtained according to Example 10 was cross-linked for 60 min. at room temperature.

.d~.~

~ C
O ~ ~ r~ c~ o o S S~ ~ ~ ~ ~
I~
C~
O O`IP
U ~ d' (~ CO t`
~t C~

C ~

C C
.~ .
~;JJ 04 N ~1 0 ~
O O

~H
~
CO ~9 ~
u~ o r~ In ~rl ~ ~ ~

C o ~ a~ m la H H H H
~ ~ H ~ H H
C ~ 2 m U~ ~, ~ ~Z C~ o ~, E~

%~
Tests to demonstrate the dependency of cross-linking time o _h_ masses according to the present invention during the cold cross-linking of esterizing catalyst (Examples 13-20) Example 13 is a comparative exarnple Eor the followiny examples in Table 6. The mass used in the test contained no cata-lyst and corresponded to the cross-linkable mass in Example 1 of Table 4, i.e., it was obtained by mixing 100 g of the binding agent IIA with 117 g of the binding agent IA at 20C

AV of binding agent IIA = 1.9 OE~ o~ binding agent IA
1~ In each instance 100 g of the binding agent IIA were mixed at 20C with a mixture of 117 g of binding agent IA and 2.5%
of a catalyst contained in Table 6, relative to the biding agent combination. Deviating from these conditions the quantity of catalyst used in Examples 19 and 20 amounted to only 0.5~.
The masses so obtained were kept at 20C. Thumb-pres-sure sampling was used to determine the shelf life after which the cross-linked mass was already solid, but still tacky on the sur-face.

7~

r~
V
C ~D ~ ~ d' ~ u~ O ~D
~ ~D r- t- ~ I` I` I` I~
C~
,~

o V
v a 11~ h ,,~ rl '~I 'r~
o ul ,C F: h h h e h h u) ~ ~ o o o In o o ~r~ Q) ~ ~ ~ ~ r~
V h ,~
~ ~e h ~
O ~
U~--' ~ e ~ ~, a) o h ~ O C
~rl ~r~ ~ X h C N O
~ r~
1- I ~I X ,C a) E~
ul ~ ~ a ~ ~ e ~ r~ s rl a) 111 a) I I N ~ Z '~Ur~l C
o a) ~D ~ (I) ` ~ ~ a ~ ~
c ) ~ Z r~
IJ O
h ~S ~ r~ U- I Z L~
~ Z O

,,~
~9 h ~ ~ u~ ~9 t` co ~ o ~ X
E~

f,/,'.~
Production of heat cross-linkable, f-i-~er-~ee masses, and cross-7~ i linking such masses (Examples 21 - 29) In each instance, 100 g of the binding agent IIA was mixed with 117 g of the binding agent IA at 20C

AV of binding agent IIA = 1.9 OHV of binding agent IA
(Compare Example 1 of Table 4) in a roller mill with a filler and in some examples with a softening oil, the kind and quantity of which is set out in the following table 7. The masses so obtained were kept at room temperature for 24 hours to enable them to degas (degassing can be completed in a much shorter time in a vacuum) and then cross-linked by being heated to 110C for three hours.
(Examples 21 to 28).
In Example 29, unlike the remaining examples in Table 7, the method used was that binding agent IIC from Table 3 was used a binding agent II.

~f~
Table 7 Example Filler Proportion Softening Oil Shore of total ~Jght Hardness A
~ i~
21 ~alc 50 36 22 Ground chalk 50 32 23 Ground chalk 25 Paraffin Oil 25 9 24 Polyethylene-powder 50 42 CaSO4.O,5 H2O 50 18 26 Soot (N330) 33 65 27 Soot (N330) 33 Aro~atic Oil 33 34 28 Pyrogenic Silicic acid 18 12 29* Pyrogenic Silicic acid 18 27 * With binding agent combination IA-IIC

Claims (16)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A cross-linkable polymer composition comprising:
(a) a binding agent which is a combination of:
(i) 10 to 90 weight % based on the combination of a binding agent I which is a functionalized 1,3-butadiene-based polymer having a number average molecular weight (?n) of 500 to 10,000 containing a primary or secondary hydroxyl group and which has a hydroxyl value of 5 to 200, and (ii) 90 to 10 weight % based on the combination of a binding agent II which is a functionalized 1,3-butadiene-based polymer having a number average molecular weight (?n) of 500 to 10,000 containing a Bernstein acid anhydride side group and which has an acid value of 10 to 300, wherein the base polymer of each of the binding agent I and the binding agent II is a 1,3-butadiene homopolymer or a copolymer of at least 70 weight % of a 1,3-butadiene and at most 30 weight % of a monomer copolymerizable with 1,3-butadiene selected from the group consisting of a 1,3-diene other than 1,3-butadiene and an alpha-olefin and the base polymer may have been isomerized, hydrogenated or cyclized;
and (b) a cross-linking amount of a carboxylic acid esterification catalyst selected from the group consisting of (alkyl)benzene-sulfonic acids, paraffin sulfonic acids and organic primary, secondary or tertiary amines which are not acyclized under the cross-linking conditions where the amines are cyclic, provided that triethylamine is excluded, wherein the binding agents and the cross-linking agent are selected such that the binding agents I and II cross-link each other without the addition of a further cross-linking agent.
2. A composition according to claim 1, wherein the binding agents I and II are in each instance present in a quantity of 20 to 80 weight % based on the combination;
the number average molecular weight (?n) of the polymer that forms the basis of the binding agents I and II is 1,000 to 8,000;
the hydroxy value of the binding agent I is 10 to 150; and the acid value of the binding agent II is 20 to 250.
3. A process for producing a cold cross-linking mass, which comprises mixing the binding agent as defined in claim 1 with a cross-linking amount of the carboxylic acid esterification catalyst as defined in claim 1.
4. A composition according to claim 1 or 2, which further comprises one or more selected from the group consisting of:
extender oils;
fillers; and additives selected from the group consisting of anti-aging agents, light-protecting agents, pigments, dyes which are soluble in the composition, adhesives, thickeners, flame retardants, smoke retardants.
5. A composition according to claim 2, which further comprises a filler which is capable of directly reacting with the anhydride groups of the binding agent II.
6. A composition according to claim 5, wherein the filler is a hydroxide, oxide, basic carbonate or carbonate of an alkaline earth metal or of zinc or a hydroxide or oxide of aluminum.
7. A composition according to claim 2, which further comprises an extender oil.
8. A composition according to claim 1, 2 or 4, wherein the catalyst is N-methylimidazole.
9. A composition according to claim 5, 6 or 7, wherein the catalyst is N-methylimidazole.
10. A composition according to claim 1,2 or 4, wherein the catalyst is a member selected from the group consisting of pyridine, 3-amino-2,4-dimethylpentane, 1,1,6,6-tetraisopropyl-2,5-diazahexane, N-methylimidazole, di-(2-ethylhexyl)amine, N,N,N',N'-tetramethylethylenediamine, and p-toluenesulfonic acid.
11. A composition according to claim 5, 6 or 7, wherein the catalyst is a member selected from the group consisting of pyridine, 3-amino-2,4-dimethylpentane, 1,1,6,6-tetraisopropyl-2,5-diazahexane, N-methylimidazole, di-(2-ethylhexyl)amine, N,N,N',N'-tetramethylethylenediamine, and p-toluenesulfonic acid.
12. A process for producing a cross-linked mass which comprises:
cross-linking a cross-linkable polymer composition comprising a binding agent which is a combination of:
(i) 10 to 90 weight % based on the combination of a binding agent I which is a functionalized 1,3-butadiene-based polymer having a number average molecular weight (?n) of 500 to 10,000 containing a primary or secondary hydroxyl group and which has a hydroxyl value of 5 to 200, and (ii) 90 to 10 weight % based on the combination of a binding agent II which is a functionalized 1,3-butadiene-based polymer having a number average molecular weight (?n) of 500 to 10,000 containing a Bernstein acid anhydride side group and which has an acid value of 10 to 300, wherein the base polymer of each of the binding agent I and the binding agent II is a 1,3-butadiene homopolymer or a copolymer of at least 70 weight % of a 1,3-butadiene and at most 30 weight % of a monomer copolymerizable with 1,3-butadiene selected from the group consisting of a 1,3-diene other than 1,3-butadiene and an alpha-olefin and the base polymer may have been isomerized, hydrogenated or cyclized, either without or under heating, wherein [A] the cross-linking without heating is performed in the presence of a cross-linking amount of a carboxylic acid esterification catalyst selected from the group consisting of (alkyl)benzenesulfonic acids, paraffin sulfonic acids and organic primary, secondary or tertiary amines which are not acyclized under the cross-linking conditions where the amines are cyclic, provided that triethyl-amine is excluded, [B] and the binding agents and the carboxylic acid esterification catalyst where needed are selected such that the binding agents I and II cross-link each other without the addition of a further cross-linking agent.
13. A process according to claim 12, wherein the cross-linking is performed in the presence of the carboxylic acid esterification catalyst at an ambient temperature or at a warm temperature up to 45°C.
14. A process according to claim 12, wherein the cross-linking is performed in the absence of the carboxylic acid esterification catalyst under heating.
15. A process according to claim 12, 13 or 14, wherein the cross-linkable polymer composition further comprises a filler.
16. A process according to claim 12, 13 or 14, wherein the cross-linkable polymer composition further comprises an extender oil.
CA000492410A 1984-10-05 1985-10-07 Heat cross-linkable polymer compositions and their production process Expired CA1248271A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5356994A (en) * 1991-07-10 1994-10-18 Bostik, Inc. Adhesive/sealant composition comprising a rubber component
US6204321B1 (en) 1993-12-17 2001-03-20 Henkel Corporation Sealant and adhesive with damping properties
US6361643B2 (en) 1994-11-23 2002-03-26 Henkel Teroson Gmbh Method for reducing mechanical vibration in metal constructions
US6448338B1 (en) 1997-07-16 2002-09-10 Henkel Teroson Gmbh Hot-setting wash-fast sealant for shell structures
US6518346B1 (en) 1998-05-23 2003-02-11 Henkel Teroson Gmbh Catalysts for producing cold or hot cross-linkable masses
WO2011140669A1 (en) * 2010-05-10 2011-11-17 3M Innovative Properties Company Flame retardant encapsulant composition

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4857563A (en) * 1987-03-09 1989-08-15 Minnesota Mining And Manufacturing Company Encapsulant compositions for use in signal transmission devices
DE3809297C1 (en) * 1988-03-19 1994-03-17 Dynamit Nobel Ag Binder for propellant bodies
JPH01254739A (en) * 1988-04-04 1989-10-11 Nippon Oil Co Ltd Cold-curing resin composition
FR2635110B1 (en) * 1988-08-05 1990-11-09 Saim Adhesifs Insonorisants Mo PREGELIFIABLE ADHESIVE
DE4219359A1 (en) * 1992-06-12 1993-12-16 Jordan Paul Eltech Potting compound and process for its manufacture
DE59403867D1 (en) * 1993-07-16 1997-10-02 Ciba Geigy Ag SINGLE-COMPONENT, STABLE AT ROOM TEMPERATURE, HEAT-CURING MEASURES FROM POLYMERS CONTAINING ANHYDRIDE GROUPS AND POWDER-BASED CROSSLINKING AGENTS, METHODS FOR THEIR PRODUCTION AND THEIR USE
DE4441656A1 (en) * 1994-11-23 1996-05-30 Teroson Gmbh Elastomer products with acoustic damping properties
DE10000957A1 (en) * 2000-01-12 2001-08-02 Jordan Paul Eltech Handicraft potting compound
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EP2105288A1 (en) * 2008-03-28 2009-09-30 Carl Freudenberg KG Self-healing elastomer system
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Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3462516A (en) * 1964-08-31 1969-08-19 Phillips Petroleum Co Blends of a liquid diene polymer and maleic anhydride copolymer
DE3070952D1 (en) * 1979-06-26 1985-09-12 British Petroleum Co Plc Cross-linked polymer compositions and production thereof
DE3163520D1 (en) * 1980-09-26 1984-06-14 British Petroleum Co Plc Cross-linked polymer compositions and production thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5356994A (en) * 1991-07-10 1994-10-18 Bostik, Inc. Adhesive/sealant composition comprising a rubber component
US6204321B1 (en) 1993-12-17 2001-03-20 Henkel Corporation Sealant and adhesive with damping properties
US6361643B2 (en) 1994-11-23 2002-03-26 Henkel Teroson Gmbh Method for reducing mechanical vibration in metal constructions
US6448338B1 (en) 1997-07-16 2002-09-10 Henkel Teroson Gmbh Hot-setting wash-fast sealant for shell structures
US6518346B1 (en) 1998-05-23 2003-02-11 Henkel Teroson Gmbh Catalysts for producing cold or hot cross-linkable masses
WO2011140669A1 (en) * 2010-05-10 2011-11-17 3M Innovative Properties Company Flame retardant encapsulant composition

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DE3436556A1 (en) 1986-04-10
ATE40394T1 (en) 1989-02-15
DK454485D0 (en) 1985-10-04
NO853930L (en) 1986-04-07
DK454485A (en) 1986-04-06
CA1305806B (en) 1992-07-28
DE3567897D1 (en) 1989-03-02

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