CA1255036A - Stable isocyanate/epoxide prepolymers and thermoset polyurethanes produced therefrom - Google Patents
Stable isocyanate/epoxide prepolymers and thermoset polyurethanes produced therefromInfo
- Publication number
- CA1255036A CA1255036A CA000515830A CA515830A CA1255036A CA 1255036 A CA1255036 A CA 1255036A CA 000515830 A CA000515830 A CA 000515830A CA 515830 A CA515830 A CA 515830A CA 1255036 A CA1255036 A CA 1255036A
- Authority
- CA
- Canada
- Prior art keywords
- isocyanate
- prepolymer
- polyisocyanate
- epoxy
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
Abstract
ABSTRACT OF THE DISCLOSURE
A process for preparing a polyurethane by reaction of A, a prepolymer prepared by the low temperature reaction of a polyisocyanate and a polyepoxide, with B, a polyol, is described.
A process for preparing a polyurethane by reaction of A, a prepolymer prepared by the low temperature reaction of a polyisocyanate and a polyepoxide, with B, a polyol, is described.
Description
~L~5~i[)3~
STABLE ISOCYANATEtEPOXIDE PREPOLYMERS AND THERMOSET
POLYURETHANES PRODUCED THEREFROM
, This invention relates to prepolymers containing - 5 both isocyanate and epoxide groups which have excellent shelf life and to thermoset polyurethane type materials which can be prepared from the prepolymers by their reaction with polyols usually in the presence of a cataly~t. The prepolymers are prepared by the low 10 temperature reaction of a polyisocyanate with a polyepoxide which contains few or no hydroxyl groups.
Reactions of polyisocyanates with polyepoxides in the presence of a suitable catalyst have been known to result in the formation of polymexs which contain 15 oxazolidone groups in the polymer backbone. Reactions of polyisocyanates or a polyisocyAnate prepolymer with a mixture of hydroxy and epoxy group containing material to produce poly (oxazolidone-urethane~
thermoset polymers have been described in U.S. Patent 20 Nos. 3,847,874 and 4,386,19:L; Japanese Patent No.
59,179 European Patent No. 129787-A and West German Patent publication No. 3,323,123.
.S. Patent No. 3,847,874 describes the formation of polymers containing oxazolidone and urethane 25 linkages by reaction of a polyisocyanate with a prepol~mer formed by a two-step reaction involving tl) reaction of a dicarboxylic acid or anhydride and saturated dihydric alcohol followed by 12) reaction with a diepoxide. Modi~ication of this is described in 30 U.S. Patent No. 4,386,191 which relates to a single step proce~s for forming epoxy and hydroxy group containing prepolymers and thermoset polymers therefrom by reacting the prepolymers wi~h polyisocyanates. The West Ge~man Patent publication No. 3,3~3,123 describe~
the formation of thermoset polymer with high mechanical and heat deformation properties from the reaction of a .
~ZS56~36 polyisocyanate with a mixture of polyol and polyepoxide in the presence of catalyst such as boron trichloride with benzyl dimethyl amine.
We have discovered that the use of a 5 polyisocyanate prepolymer prepared from the low temperature reaction of a polyisocyanate, such as methylene bis (phenyl isocyanate) with a polyepoxide containing no or very low levels of hydroxyl groups (less than 20~ by weight based cn the epoxy groups 10 present~ which has a long shelf stability, in the poly (oxazolidoneJurethane) thermoset polymer synthesis by reacting said prepolymer with polyols in the presence of a catalyst which promotes the formation of urethane/isocyanurate/oxazolidone groupings.
lS The most suitable epoxy materials, for use in th~
~ resin systems of the invention are resins having an ; epoxide equivalent number of 2.0 or greater. Included are biæphenol A-based epoxy resins Ruch as bisphenol-A
diglycidyl ether, bi~phenol-~ diglycidyl ether, aliphatic epoxides, cycloaliphatic epoxides, epoxy novalak and heterocyelic-~ype epoxy resinsO The~e should, as previously noted, be subs~ntially free of hydroxyl groups.
Polyols useful in the preparation of the thermoset polymers of this invention include thosa having at least two hydroxyl yroups per molecule and having equivalent weights falling in the range of from 20 to S000. Specific polyols include butane diol, cyclohexane dimethanol, tripropylene glycol, amide diols, urethane diols, polyether polyols such as poly itetramethylene ether) diols, poly (propylene ether) - polyols, polyester polyols, and the like.
Polyhydroxy polyethers are suitable. Polyhydroxy polyethers can be prepared by polymeri~atlon of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or ~2~ 36 epichlorohydrin either on their own or by chemical addition to other materials. Suitable other materials include ethylene glycol, propylene glycol, trimethylol propanes and 4,4'-dihydroxy diphenyl propane. 5ucrose 5 polyethers also may be used. Polybutadienes having - hydroxyl yroups as well as other known hydroxyl ~ containing vinyl addition polymerized polymers can be used.
According to the present invention/ hydroxyl 10 containing polyesters; polythioethers, polyacetals, polycarbonates or polyesteramides of the types known for the formation of polyurethanes may also be used.
Particularly useful polyols for the present invention include the following representative 15 aliphatic and aromatic polyhydric alcohols. Ethylene glycol~ propylene glycol, trimethylene glycol~
triethylene glycol, pentaethylene glycol, polyethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 2,2-dimethyl-1,3-pxopanediol, hexamethylene 20 glycol, 1,4,cyclohexane dimethanQl, xylene alcohols, ethyl resorcinol, propyl resorcinol, 2,4-dimethyl xesorcinol t 3,6-dimethyl-1~2-dihydroxy naphthalene, 3-methyl-1,4,5-naphthalene triol, dimethylol toluene, dimethylol xylene, bis hydroxyethyl or ; 25 biswhydroxypropyl ethers of resorcinol, catechol and hydroquinone, 1,5-dihydroxy naphthalene, 4,4'-isopropylidene-bis-phenol~ and the like.
The polyisocyanates useful in the preparation of the prepolymers of this invention include organic isocyanates having at least two isocyanate groups per molecule. The polyisocyanates can be o~ low, high or intermediate molecular weight and can be any of a wide vari~ky vf organic polyisocyanates including ethylene diisocyanate, trimethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, tetraethylene diisocyanate, pentamethylene diisocyanate, propylene-1,2-diisocyanate, 2,3-dimethyl tetramethylene diisocyanate, butylene-1,2-diisocyanate, butylene-1,3-diisocyanate, 1,4-diisocyanate - 5 cyclohexane, cyclopentene-1,3-diisocyanate, p-phenylene diisocyanate, l-methyl phenylene-2,4-diisocyanate;
naththalene-1,4-diisocyanate, toluene diisocyanate, diphenyl-4,4~-diisocyanate, benzene-1,2,4-triisocyanate, xylene-1,4-diisocyanate, : 10 xylene-1,3-diisocyanate, 4,4'diphenylene methane diisocyanate, 4,4'-diphenylene propane diisocyanate, 1,2,3,4-tetraisocyanate butane, butane-1,2,3-triisocyanate, polymethylene polyphenyl isocyanate, and other polyisocyanates having an 1~ isocyanate functionality of at least two more fully disclosed in U.S. Patent Numbers 3,350,362 and ; 3,382,215. Polyisocyanates which are polymeric in nature including isocyanate prepolymers of all types are included in this invention.
Thus, it has been found that polyisocyanate prepolymers ob~ained from the reaction of di-or polyi~ocyanates with polyepoxides haviny no or low levels of hydroxy functionality at temperatures ~elow about 100 degrees C. in the absence of any catalyst 25 contain both isocyanate and epoxide groups and these liquid prepolymers have long shelf stability. To illustrate, when a mixture of 80-90% polyisocyanate (liquid methylene bis-phenyl isocyanate having an isocyanate equivalent weight of 144) and 10-20~ of a liquid diglycidyl ether of Bisphenol-A (epoxy equivalent weight of 180-190~ is heated at about 60 - degrees C. ~or about 3 hours, a li~uid prepolymer i5 foxmed which has a shelf stability a~ room temperature of more than 2 months. This prepolymer, upon reaction with a polyol which contains a tertiary amine and oationic complex catalyst, result~ in the formation of ..... . .. . .. .. .
~ %s~
a thermoset polymer whieh contains urethane, isocyanurate and oxazolidone linXages. Isocyanurate and oxazolidone groups in the polymer are believed to im~art high h~at deformation and thermal stability properties 2nd the urethane linkages are believed to provide the toughness and flexibility to the polymer.
In order to improve the impact strength of the thermoset polymer it is advantageous to add to the - polymerization mixture soft segments such as a 10 ~ynthetic rubber.
The equivalent ratio of isocyanate to epoxy groups in the polyisoc~anate-epoxy prepolymer compositions may be in the range of from 1:0.001 to 1:1 and pre~erably from 1:0.05 to 1:0.5. The reaction of polyisocyanate 15 and polyepoxide to form a prepolymer can be carried out at temperatures in the range of from about room ; temperature to about 100 deyrees C. The equivalent ratio of isocyanate to combined epoxy and hydroxyl groups may ~e in the range of from 0.8:1 to 3:1. The 20 suitable catalysts for the thermoset polymer formation include cationic catalysts, tetraalkyl ammonium salts tertiary amines, titanium alkoxides, alkali and alkaline earth metal salts, boron trihalide-tertiary amine adducts, organotin compounds, and others known to 25 those skilled in the art.
Tha prepolymers and the thermoset polymers of this invention can contain the usual fillers, pigments, and the like which are well known to those skilled in the art.
The polymerization temperature used in the preparation of the thermoset polymers of this invention can range from a~out room temperature to about 200 degrees C.
This invention is ~urther illustrated in the followin~ representative examples.
.
-- . . ~ -- .
~;~S5~;3 6 } b , The polyisocyanate-polyepoxy prepolymers were i prepared by reacting either the polyisocyanate with polyepoxide or reacting a polyisocyanate prepolymer prepared from the polyisocyanate reaction with high molecular weight polyol or polybutadiene rubber (hydroxy or carboxylic acid terminated). The procedures used are described in more detail below.
A~ Liquid methylene bis (phenyl isocyanate) - 10 (700g) and 70g of carboxylic acid terminated polybutadiene rubber (Hycar 1300 x 8 from BF Goodrich Co.) were mixed and heated at g6 to 100 degrees C. for about 3 hours to give the polyisocyanate prepolymer.
B. Liquid methylene bis (phenyl isocyanate3 ~700g) and 70g of carboxylic acid terminated polybutadiene rubber were mixed and heated at 95 to 100 degrees C. for 3 hours. The mixture was then brought to a~out 80 degrees C. and to this was added 77g of liquid diglycidyl ether of Bisphenol-A(DGEBA) ; ~o (equivalent weight of 180-183, Epon 826*from Shell Chemical Co.). The resulting mixture was heated f3r 1 ; hour at 80 degrees C. to give a prepolymer containing epoxy and isocyanate groups.
C. The procedure of B was followed using 700g of liquid diisocyanate, 70g of the polybutadiene rubber and 77g of liquid D~EBA lequ~valent weight Df 185-192, Epon 828 from Shell Chemical Co.) to give the liquid prepolymer which contained both isocyanate and epoxide l groups.
; 3~ D. The procedure of A was fo~lowed using 400g of t~e diisocyanate and 40g of poly BD 45 MT (hydroxy terminated polybutadiene ~rom Arco Chemical Co,) to give a clear solution o~ polyisocyanate prepolymer.
E. The procedure of B wa~ followed using 400g of the liquid diisocyanate, 40g o~ poly BD 45 ~T and 44g o~ liquid DGEBA I~Epon 82S) to giYe thP liquid *Tr~de Mar~s ... . . . , . .... .. _ .. _ .. . .. .. . . . . .. ..
~2SS;~36 prepolymer which contained both isocyanate and epoxide groups.
E~. Liquid methylene bis (phenyl isocyanate) (300gj and 53g of liquid DGEBA IEPon 826~ were mixed 5 and heated at 80 degrees C. for 1 hour. The xesulting clear polyisocyanate prepolymer was kept at room temperature for approximately 2 months during which time no significant change in the viscosity was noticed and the solution remained liquid without any gelation.
10 This material contained both isocyanate and epoxy groups.
i EX~MPLE 2 A mixture of 15.0g of dipropylene glycol (DPG), 15 3.5g of trimethylol propane ~TMP), 1.8g of a bicyclic amide acetal having the formula H~
(moisture scavenger) and 0.6g of methyl trioctyl ammonîum chloride ~catalyst) was degassed on a rotary evaporator under reduced pres~ure and was mixed with 65g of the degassed polisocyanate/epoxy prepolymer of Example l B. The resulting mixture was poured into a mold prepared by two silicone mo~d release coated parallel glass plates held apart ~y l/8 inch thickness spacers, The mold was placed in an oven at 60 degrees ; 3~ C. and the temperat~re of the oven was gradually increased to 130 degrees C. over a 2 hour period. The - resul~ing polymer sheet was further postcured at lO0 degrees C. for 1 hour. The solid polymer which resulted was found to have a notched i~od impact strength (ASTM-D256) of 1.3 foot pounds~inch of notch, an unnotched izod impact strength of 10.3 foot .. ..
~5563 36 pounds/inch, a heat distortion temperature (ASTM-D648) of 118 degrees C., a yield strength ~ASTM-D790) of 17,762.psi and a flexural modulus of 361,193 psi. The Tg by DSC (differential scanning calorimetry) was 132.5 5 degrees C. and 10~ weight loss by thermal gravimetric analysis ~TGA) in nitrogen occurred at 311 degrees C.
This example, which is outside the scope of this 10 invention, is for comparison purposesO No apoxy resin was used in the process.
The procedure of Example 2 was followed using a mixture of 35.1g of DPG, 8.1g of TMP, 0.7g of the bicyclic amide acetal and allowing this mixture to lS react with 134g of the polyisocyanate prepolymer of ; Example 1 A. The postcured polymer was found to have a notched izod impast strengt:h of 0.3 foot pounds/inch of notch, an unnotched izod impact strength of 0.5 foot pounds/in~h and a heat distortion temperature of 80 20 degreeS C.
EXAM~LE 4 The procedure of Exampla 2 was followed using 22~9g of DPG, 5.4g of TMP, 0.83g of the catalyst and lOOg of the polyisocyanate/epoxy prepolymer of Exampl~
1 C. The resulting polymer was found to have a notched ~zod impact strength of 1.1 foot poundsfinch o~ notch and a heat distortion temperature of 114 degrees C.
The procedura of Example 2 was followed using 30.8g o ~P~, 0~83g of catalyst and lOOg of the ; prepolymer of Example lC. The resulting polymer was found to have a notched izod impact strength of 1.4 foot pounds/inch of nokchr an unnotched izod impact .. . . . . .
~255~36 g strength of greater than 14 foot pounds/inch and a heat distortion temperature of 101 degrees CO
The procedure of Example 2 was followed except that no catalyst was used. The reaction charge was - 22.9g of DPG, 5.4g of TMP, and lOOg of the prepolymer of Example 1 C. The resulting polymer was found to have a notched izod impact strength of 1.2 foot - 10 pounds/inch of notch and a heat distortion temperature of 80 degrees C. This indicates that when the oxazolidone/isocyanurate catalyst is not used a somewhat inferior product results (compare with Example 4~.
; The procedure of Example 2 was followed using 17.4g of DPG, 3.6g of TMP, O.5g of bicyclic amide acetal, 0.6g of the catalyst and 75g of the epoxy/
20 isocyanate prepolymer of Example 1 E. The resulting polymer was found to have a :notched izod impact ; strength of 0.6 foot pounds~inch of notch, an unnotched : izod impact ~trength of 10.2 foot pounds/inch, a heat distortion temperature of 110 deqrees C/. a tensile 25 yield strength of 18,282 psi and a flexural strength of 365,65fi psi.
The procedure of Example 7 was repeated except that no catalyst was used. The resulting polymer was found to have a notched izod impact strength of 0.5 foot pounds~inch of notch, an unnotched izod impact : strength of 8.0 foot pounds/inch, and A heat distor~ion temperature of 84 degrees C.
~L;Zt5~36 .` ~This example is for comparison purposes and is outside the scope of the present invention. ~he r procedure of Example 2 was followed using the charge r, 5 ratio similar to that of Example 7 except that the prepolymer used contained no epoxy groups~ The reaction charge was 21~5g of DPG, 4.5g of TMP, l.Og of bicyclic amide acetal and 82~5g of the isocyanate propolym~r of Example 1 D. The resulting polymer was 10 found to have a notched izod impact strength of 0.5 foot pounds/inch of notch and a heat distortion temperature of 76 degrees C.
The procedure of Example ~ was followed using 26.4g of DPG, 6.lg of TMP, l.Og of the bicyclic amide acetal, 7.5g of the carboxyl:ic acid terminated ~ycar rubber, O.9g of catalyst and lOOg of the ! isocyanate/epoxy prepolymer of Example 1 F. The .' 20 resulting polymer was found 1:o have a notched izod A impact strength of 1. 0 foot pounds~inch of notch and a heat distortion temperature of 108 degrees C.
25 ~he procedure of Example 2 was followed using 14.5g o~ DPG, 8g of propylene glycol, 12g of grafted poly (styreneJacrylonitrile) polyol ~Niax*34~28,2000 equivalent weight triol from Union Carbide Co.), and 90g of the isocyanate/epoxy prepolymer o~ Example 1 F.
The resulting polymer was found to have a notched izod impact strength of 0.9 foot pounds/inch of notchr an unnotched ~zod impact strength of 13 foot pounds/inch, a heat dist~rtion temperature of 100 degrees C., a yleld ~trength o 18,053 psi and a flexural modulu~ of 374,173 psi.
*Tr~de Mark ........ ... .. . .. .... ... .. . .... . . .
~2~ 3~i The procedure of Example 2 was followed using 24.3g of DPG, 5.4g of TMP, 0.85g of catalyst and lOOg of the isocyanatetepoxy prepolymer of Example 1 F~ The S resulting polymer was found to have a notched izod impact strength of 0.6 foot pounds/inch of notch and a heat distortion temperature of 107 degrees C.
10The degassed solution of 34.5g of DPG, 8.1g of TMP, 1.Og of the bicyclic amide acetal and 1.3g of the catalyst of Example 2 was mixed with 150g of the degassed isocyanate/epoxy prepolymer of Example 1 B.
The resulting mixture was injected on*o a glass mat 15 placed in a mold prepared by two parallel Teflon plates held apart by 1/8 inch spacers. The mold was placed in ; an oven at 100 degrees C. for one hour, followed by 120 degrees C. for another hour. The resulting glass r~inforced (27~ glass) polymer was found to have a notched izod impact strength of 7.6 foot pounds/inch of notch, a yield strength of 29,245 psi and a flexural modulus of 823,725 psi.
STABLE ISOCYANATEtEPOXIDE PREPOLYMERS AND THERMOSET
POLYURETHANES PRODUCED THEREFROM
, This invention relates to prepolymers containing - 5 both isocyanate and epoxide groups which have excellent shelf life and to thermoset polyurethane type materials which can be prepared from the prepolymers by their reaction with polyols usually in the presence of a cataly~t. The prepolymers are prepared by the low 10 temperature reaction of a polyisocyanate with a polyepoxide which contains few or no hydroxyl groups.
Reactions of polyisocyanates with polyepoxides in the presence of a suitable catalyst have been known to result in the formation of polymexs which contain 15 oxazolidone groups in the polymer backbone. Reactions of polyisocyanates or a polyisocyAnate prepolymer with a mixture of hydroxy and epoxy group containing material to produce poly (oxazolidone-urethane~
thermoset polymers have been described in U.S. Patent 20 Nos. 3,847,874 and 4,386,19:L; Japanese Patent No.
59,179 European Patent No. 129787-A and West German Patent publication No. 3,323,123.
.S. Patent No. 3,847,874 describes the formation of polymers containing oxazolidone and urethane 25 linkages by reaction of a polyisocyanate with a prepol~mer formed by a two-step reaction involving tl) reaction of a dicarboxylic acid or anhydride and saturated dihydric alcohol followed by 12) reaction with a diepoxide. Modi~ication of this is described in 30 U.S. Patent No. 4,386,191 which relates to a single step proce~s for forming epoxy and hydroxy group containing prepolymers and thermoset polymers therefrom by reacting the prepolymers wi~h polyisocyanates. The West Ge~man Patent publication No. 3,3~3,123 describe~
the formation of thermoset polymer with high mechanical and heat deformation properties from the reaction of a .
~ZS56~36 polyisocyanate with a mixture of polyol and polyepoxide in the presence of catalyst such as boron trichloride with benzyl dimethyl amine.
We have discovered that the use of a 5 polyisocyanate prepolymer prepared from the low temperature reaction of a polyisocyanate, such as methylene bis (phenyl isocyanate) with a polyepoxide containing no or very low levels of hydroxyl groups (less than 20~ by weight based cn the epoxy groups 10 present~ which has a long shelf stability, in the poly (oxazolidoneJurethane) thermoset polymer synthesis by reacting said prepolymer with polyols in the presence of a catalyst which promotes the formation of urethane/isocyanurate/oxazolidone groupings.
lS The most suitable epoxy materials, for use in th~
~ resin systems of the invention are resins having an ; epoxide equivalent number of 2.0 or greater. Included are biæphenol A-based epoxy resins Ruch as bisphenol-A
diglycidyl ether, bi~phenol-~ diglycidyl ether, aliphatic epoxides, cycloaliphatic epoxides, epoxy novalak and heterocyelic-~ype epoxy resinsO The~e should, as previously noted, be subs~ntially free of hydroxyl groups.
Polyols useful in the preparation of the thermoset polymers of this invention include thosa having at least two hydroxyl yroups per molecule and having equivalent weights falling in the range of from 20 to S000. Specific polyols include butane diol, cyclohexane dimethanol, tripropylene glycol, amide diols, urethane diols, polyether polyols such as poly itetramethylene ether) diols, poly (propylene ether) - polyols, polyester polyols, and the like.
Polyhydroxy polyethers are suitable. Polyhydroxy polyethers can be prepared by polymeri~atlon of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or ~2~ 36 epichlorohydrin either on their own or by chemical addition to other materials. Suitable other materials include ethylene glycol, propylene glycol, trimethylol propanes and 4,4'-dihydroxy diphenyl propane. 5ucrose 5 polyethers also may be used. Polybutadienes having - hydroxyl yroups as well as other known hydroxyl ~ containing vinyl addition polymerized polymers can be used.
According to the present invention/ hydroxyl 10 containing polyesters; polythioethers, polyacetals, polycarbonates or polyesteramides of the types known for the formation of polyurethanes may also be used.
Particularly useful polyols for the present invention include the following representative 15 aliphatic and aromatic polyhydric alcohols. Ethylene glycol~ propylene glycol, trimethylene glycol~
triethylene glycol, pentaethylene glycol, polyethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 2,2-dimethyl-1,3-pxopanediol, hexamethylene 20 glycol, 1,4,cyclohexane dimethanQl, xylene alcohols, ethyl resorcinol, propyl resorcinol, 2,4-dimethyl xesorcinol t 3,6-dimethyl-1~2-dihydroxy naphthalene, 3-methyl-1,4,5-naphthalene triol, dimethylol toluene, dimethylol xylene, bis hydroxyethyl or ; 25 biswhydroxypropyl ethers of resorcinol, catechol and hydroquinone, 1,5-dihydroxy naphthalene, 4,4'-isopropylidene-bis-phenol~ and the like.
The polyisocyanates useful in the preparation of the prepolymers of this invention include organic isocyanates having at least two isocyanate groups per molecule. The polyisocyanates can be o~ low, high or intermediate molecular weight and can be any of a wide vari~ky vf organic polyisocyanates including ethylene diisocyanate, trimethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, tetraethylene diisocyanate, pentamethylene diisocyanate, propylene-1,2-diisocyanate, 2,3-dimethyl tetramethylene diisocyanate, butylene-1,2-diisocyanate, butylene-1,3-diisocyanate, 1,4-diisocyanate - 5 cyclohexane, cyclopentene-1,3-diisocyanate, p-phenylene diisocyanate, l-methyl phenylene-2,4-diisocyanate;
naththalene-1,4-diisocyanate, toluene diisocyanate, diphenyl-4,4~-diisocyanate, benzene-1,2,4-triisocyanate, xylene-1,4-diisocyanate, : 10 xylene-1,3-diisocyanate, 4,4'diphenylene methane diisocyanate, 4,4'-diphenylene propane diisocyanate, 1,2,3,4-tetraisocyanate butane, butane-1,2,3-triisocyanate, polymethylene polyphenyl isocyanate, and other polyisocyanates having an 1~ isocyanate functionality of at least two more fully disclosed in U.S. Patent Numbers 3,350,362 and ; 3,382,215. Polyisocyanates which are polymeric in nature including isocyanate prepolymers of all types are included in this invention.
Thus, it has been found that polyisocyanate prepolymers ob~ained from the reaction of di-or polyi~ocyanates with polyepoxides haviny no or low levels of hydroxy functionality at temperatures ~elow about 100 degrees C. in the absence of any catalyst 25 contain both isocyanate and epoxide groups and these liquid prepolymers have long shelf stability. To illustrate, when a mixture of 80-90% polyisocyanate (liquid methylene bis-phenyl isocyanate having an isocyanate equivalent weight of 144) and 10-20~ of a liquid diglycidyl ether of Bisphenol-A (epoxy equivalent weight of 180-190~ is heated at about 60 - degrees C. ~or about 3 hours, a li~uid prepolymer i5 foxmed which has a shelf stability a~ room temperature of more than 2 months. This prepolymer, upon reaction with a polyol which contains a tertiary amine and oationic complex catalyst, result~ in the formation of ..... . .. . .. .. .
~ %s~
a thermoset polymer whieh contains urethane, isocyanurate and oxazolidone linXages. Isocyanurate and oxazolidone groups in the polymer are believed to im~art high h~at deformation and thermal stability properties 2nd the urethane linkages are believed to provide the toughness and flexibility to the polymer.
In order to improve the impact strength of the thermoset polymer it is advantageous to add to the - polymerization mixture soft segments such as a 10 ~ynthetic rubber.
The equivalent ratio of isocyanate to epoxy groups in the polyisoc~anate-epoxy prepolymer compositions may be in the range of from 1:0.001 to 1:1 and pre~erably from 1:0.05 to 1:0.5. The reaction of polyisocyanate 15 and polyepoxide to form a prepolymer can be carried out at temperatures in the range of from about room ; temperature to about 100 deyrees C. The equivalent ratio of isocyanate to combined epoxy and hydroxyl groups may ~e in the range of from 0.8:1 to 3:1. The 20 suitable catalysts for the thermoset polymer formation include cationic catalysts, tetraalkyl ammonium salts tertiary amines, titanium alkoxides, alkali and alkaline earth metal salts, boron trihalide-tertiary amine adducts, organotin compounds, and others known to 25 those skilled in the art.
Tha prepolymers and the thermoset polymers of this invention can contain the usual fillers, pigments, and the like which are well known to those skilled in the art.
The polymerization temperature used in the preparation of the thermoset polymers of this invention can range from a~out room temperature to about 200 degrees C.
This invention is ~urther illustrated in the followin~ representative examples.
.
-- . . ~ -- .
~;~S5~;3 6 } b , The polyisocyanate-polyepoxy prepolymers were i prepared by reacting either the polyisocyanate with polyepoxide or reacting a polyisocyanate prepolymer prepared from the polyisocyanate reaction with high molecular weight polyol or polybutadiene rubber (hydroxy or carboxylic acid terminated). The procedures used are described in more detail below.
A~ Liquid methylene bis (phenyl isocyanate) - 10 (700g) and 70g of carboxylic acid terminated polybutadiene rubber (Hycar 1300 x 8 from BF Goodrich Co.) were mixed and heated at g6 to 100 degrees C. for about 3 hours to give the polyisocyanate prepolymer.
B. Liquid methylene bis (phenyl isocyanate3 ~700g) and 70g of carboxylic acid terminated polybutadiene rubber were mixed and heated at 95 to 100 degrees C. for 3 hours. The mixture was then brought to a~out 80 degrees C. and to this was added 77g of liquid diglycidyl ether of Bisphenol-A(DGEBA) ; ~o (equivalent weight of 180-183, Epon 826*from Shell Chemical Co.). The resulting mixture was heated f3r 1 ; hour at 80 degrees C. to give a prepolymer containing epoxy and isocyanate groups.
C. The procedure of B was followed using 700g of liquid diisocyanate, 70g of the polybutadiene rubber and 77g of liquid D~EBA lequ~valent weight Df 185-192, Epon 828 from Shell Chemical Co.) to give the liquid prepolymer which contained both isocyanate and epoxide l groups.
; 3~ D. The procedure of A was fo~lowed using 400g of t~e diisocyanate and 40g of poly BD 45 MT (hydroxy terminated polybutadiene ~rom Arco Chemical Co,) to give a clear solution o~ polyisocyanate prepolymer.
E. The procedure of B wa~ followed using 400g of the liquid diisocyanate, 40g o~ poly BD 45 ~T and 44g o~ liquid DGEBA I~Epon 82S) to giYe thP liquid *Tr~de Mar~s ... . . . , . .... .. _ .. _ .. . .. .. . . . . .. ..
~2SS;~36 prepolymer which contained both isocyanate and epoxide groups.
E~. Liquid methylene bis (phenyl isocyanate) (300gj and 53g of liquid DGEBA IEPon 826~ were mixed 5 and heated at 80 degrees C. for 1 hour. The xesulting clear polyisocyanate prepolymer was kept at room temperature for approximately 2 months during which time no significant change in the viscosity was noticed and the solution remained liquid without any gelation.
10 This material contained both isocyanate and epoxy groups.
i EX~MPLE 2 A mixture of 15.0g of dipropylene glycol (DPG), 15 3.5g of trimethylol propane ~TMP), 1.8g of a bicyclic amide acetal having the formula H~
(moisture scavenger) and 0.6g of methyl trioctyl ammonîum chloride ~catalyst) was degassed on a rotary evaporator under reduced pres~ure and was mixed with 65g of the degassed polisocyanate/epoxy prepolymer of Example l B. The resulting mixture was poured into a mold prepared by two silicone mo~d release coated parallel glass plates held apart ~y l/8 inch thickness spacers, The mold was placed in an oven at 60 degrees ; 3~ C. and the temperat~re of the oven was gradually increased to 130 degrees C. over a 2 hour period. The - resul~ing polymer sheet was further postcured at lO0 degrees C. for 1 hour. The solid polymer which resulted was found to have a notched i~od impact strength (ASTM-D256) of 1.3 foot pounds~inch of notch, an unnotched izod impact strength of 10.3 foot .. ..
~5563 36 pounds/inch, a heat distortion temperature (ASTM-D648) of 118 degrees C., a yield strength ~ASTM-D790) of 17,762.psi and a flexural modulus of 361,193 psi. The Tg by DSC (differential scanning calorimetry) was 132.5 5 degrees C. and 10~ weight loss by thermal gravimetric analysis ~TGA) in nitrogen occurred at 311 degrees C.
This example, which is outside the scope of this 10 invention, is for comparison purposesO No apoxy resin was used in the process.
The procedure of Example 2 was followed using a mixture of 35.1g of DPG, 8.1g of TMP, 0.7g of the bicyclic amide acetal and allowing this mixture to lS react with 134g of the polyisocyanate prepolymer of ; Example 1 A. The postcured polymer was found to have a notched izod impast strengt:h of 0.3 foot pounds/inch of notch, an unnotched izod impact strength of 0.5 foot pounds/in~h and a heat distortion temperature of 80 20 degreeS C.
EXAM~LE 4 The procedure of Exampla 2 was followed using 22~9g of DPG, 5.4g of TMP, 0.83g of the catalyst and lOOg of the polyisocyanate/epoxy prepolymer of Exampl~
1 C. The resulting polymer was found to have a notched ~zod impact strength of 1.1 foot poundsfinch o~ notch and a heat distortion temperature of 114 degrees C.
The procedura of Example 2 was followed using 30.8g o ~P~, 0~83g of catalyst and lOOg of the ; prepolymer of Example lC. The resulting polymer was found to have a notched izod impact strength of 1.4 foot pounds/inch of nokchr an unnotched izod impact .. . . . . .
~255~36 g strength of greater than 14 foot pounds/inch and a heat distortion temperature of 101 degrees CO
The procedure of Example 2 was followed except that no catalyst was used. The reaction charge was - 22.9g of DPG, 5.4g of TMP, and lOOg of the prepolymer of Example 1 C. The resulting polymer was found to have a notched izod impact strength of 1.2 foot - 10 pounds/inch of notch and a heat distortion temperature of 80 degrees C. This indicates that when the oxazolidone/isocyanurate catalyst is not used a somewhat inferior product results (compare with Example 4~.
; The procedure of Example 2 was followed using 17.4g of DPG, 3.6g of TMP, O.5g of bicyclic amide acetal, 0.6g of the catalyst and 75g of the epoxy/
20 isocyanate prepolymer of Example 1 E. The resulting polymer was found to have a :notched izod impact ; strength of 0.6 foot pounds~inch of notch, an unnotched : izod impact ~trength of 10.2 foot pounds/inch, a heat distortion temperature of 110 deqrees C/. a tensile 25 yield strength of 18,282 psi and a flexural strength of 365,65fi psi.
The procedure of Example 7 was repeated except that no catalyst was used. The resulting polymer was found to have a notched izod impact strength of 0.5 foot pounds~inch of notch, an unnotched izod impact : strength of 8.0 foot pounds/inch, and A heat distor~ion temperature of 84 degrees C.
~L;Zt5~36 .` ~This example is for comparison purposes and is outside the scope of the present invention. ~he r procedure of Example 2 was followed using the charge r, 5 ratio similar to that of Example 7 except that the prepolymer used contained no epoxy groups~ The reaction charge was 21~5g of DPG, 4.5g of TMP, l.Og of bicyclic amide acetal and 82~5g of the isocyanate propolym~r of Example 1 D. The resulting polymer was 10 found to have a notched izod impact strength of 0.5 foot pounds/inch of notch and a heat distortion temperature of 76 degrees C.
The procedure of Example ~ was followed using 26.4g of DPG, 6.lg of TMP, l.Og of the bicyclic amide acetal, 7.5g of the carboxyl:ic acid terminated ~ycar rubber, O.9g of catalyst and lOOg of the ! isocyanate/epoxy prepolymer of Example 1 F. The .' 20 resulting polymer was found 1:o have a notched izod A impact strength of 1. 0 foot pounds~inch of notch and a heat distortion temperature of 108 degrees C.
25 ~he procedure of Example 2 was followed using 14.5g o~ DPG, 8g of propylene glycol, 12g of grafted poly (styreneJacrylonitrile) polyol ~Niax*34~28,2000 equivalent weight triol from Union Carbide Co.), and 90g of the isocyanate/epoxy prepolymer o~ Example 1 F.
The resulting polymer was found to have a notched izod impact strength of 0.9 foot pounds/inch of notchr an unnotched ~zod impact strength of 13 foot pounds/inch, a heat dist~rtion temperature of 100 degrees C., a yleld ~trength o 18,053 psi and a flexural modulu~ of 374,173 psi.
*Tr~de Mark ........ ... .. . .. .... ... .. . .... . . .
~2~ 3~i The procedure of Example 2 was followed using 24.3g of DPG, 5.4g of TMP, 0.85g of catalyst and lOOg of the isocyanatetepoxy prepolymer of Example 1 F~ The S resulting polymer was found to have a notched izod impact strength of 0.6 foot pounds/inch of notch and a heat distortion temperature of 107 degrees C.
10The degassed solution of 34.5g of DPG, 8.1g of TMP, 1.Og of the bicyclic amide acetal and 1.3g of the catalyst of Example 2 was mixed with 150g of the degassed isocyanate/epoxy prepolymer of Example 1 B.
The resulting mixture was injected on*o a glass mat 15 placed in a mold prepared by two parallel Teflon plates held apart by 1/8 inch spacers. The mold was placed in ; an oven at 100 degrees C. for one hour, followed by 120 degrees C. for another hour. The resulting glass r~inforced (27~ glass) polymer was found to have a notched izod impact strength of 7.6 foot pounds/inch of notch, a yield strength of 29,245 psi and a flexural modulus of 823,725 psi.
Claims (8)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. The process for preparing a polyurethane comprising reacting A. A prepolymer prepared by the low temperature reaction of a polyisocyanate and a polyepoxide containing no or very low levels of hydroxyl groups in the absence of any catalyst with B. A polyol.
2. The process of claim 1 in which A is carried out at a temperature in the range of from about room temperature to about 100°C.
3. The process of claim 2 wherein the polyepoxide contains less than 20% by weight of hydroxyl groups based on the weight of epoxy groups.
4. The process of claim 3 wherein the equivalent ratio of isocyanate to epoxy groups in the prepolymer of A is in the range of from 1:0.001 to 1:1.
5. The process of claim 3 wherein the equivalent ratio of isocyanate to combined epoxy and hydroxy groups is in the range of from 0.8:1 to 3:1.
6. The process of claim 1 A and B carried out at a temperature in the range of from about room temperature to about 200°C.
7. The process of claim 5 wherein the polyisocyanate is methylene bis(phenyl isocyanate), the polyepoxide is the diglycidyl ether of bisphenol-A, and the polyol is a mixture of dipropylene glycol and trimethylol propane.
8. The polymer prepared according to the process of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/764,284 US4614786A (en) | 1985-08-12 | 1985-08-12 | Stable isocyanate/epoxide prepolymers and thermoset polyurethanes produced therefrom |
| US764,284 | 1985-08-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1255036A true CA1255036A (en) | 1989-05-30 |
Family
ID=25070252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000515830A Expired CA1255036A (en) | 1985-08-12 | 1986-08-12 | Stable isocyanate/epoxide prepolymers and thermoset polyurethanes produced therefrom |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4614786A (en) |
| EP (1) | EP0217037A3 (en) |
| JP (1) | JPS6289717A (en) |
| CA (1) | CA1255036A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4731428A (en) * | 1986-11-03 | 1988-03-15 | American Cyanamid Co. | Epoxidized isocyanates and process for their preparation |
| US4728710A (en) * | 1986-11-28 | 1988-03-01 | Ashland Oil, Inc. | Sag resistant urethane adhesives with improved antifoaming property |
| US4737565A (en) * | 1987-04-09 | 1988-04-12 | Ashland Oil, Inc. | Single component, latent curing epoxy resin composition |
| US4757125A (en) * | 1987-07-08 | 1988-07-12 | Ashland Oil, Inc. | Bicyclic amide acetal-based cure accelerators for amine curing of epoxy compositions |
| DE3836598A1 (en) * | 1988-10-27 | 1990-05-03 | Bayer Ag | REACTIVE SYSTEMS AND A METHOD FOR PRODUCING POLYURETHANE PLASTICS |
| US5677412A (en) * | 1994-02-17 | 1997-10-14 | E. I. Du Pont De Nemours And Company | Preparation of poly(ether-urethanes) from cyclic ethers and organic isocyanates |
| DE69611777T2 (en) * | 1995-11-16 | 2001-05-31 | Nok Corp | Polyetherester elastomer mixture for sealing sleeve of a homokinetic coupling. |
| US6291577B1 (en) | 2000-04-11 | 2001-09-18 | Rhodia Inc. | Method for scavenging moisture in polyisocyanates and formulations thereof |
| US6645088B2 (en) * | 2001-04-13 | 2003-11-11 | Acushnet Company | Reaction injection moldable compositions, methods for making same, and resultant golf articles |
| US20210253772A1 (en) * | 2020-02-18 | 2021-08-19 | Covestro Llc | Polyoxazolidinone compositions |
| US20230416521A1 (en) * | 2020-12-08 | 2023-12-28 | Toray Industries, Inc. | Thermosetting epoxy resin composition, molded article from thermosetting epoxy resin, molding material for fiber-reinforced composite material, fiber-reinforced composite material, and method for producing fiber-reinforced composite material |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3313747A (en) * | 1964-10-29 | 1967-04-11 | Baker Chem Co J T | Polymers prepared from isocyanateoxazolidinones |
| JPS4940863B1 (en) * | 1970-01-22 | 1974-11-06 | ||
| US3817938A (en) * | 1971-02-12 | 1974-06-18 | K Ashida | Polyoxazolidone catalyst |
| JPS554464B2 (en) * | 1974-09-26 | 1980-01-30 | ||
| JPS5139664A (en) * | 1974-09-27 | 1976-04-02 | Mitsubishi Chem Ind | OKISAZORIDONKANOJUSURUKAGOBUTSU NO SEIZOHO |
| US4022721A (en) * | 1974-09-26 | 1977-05-10 | Mitsubishi Chemical Industries Ltd. | Process for producing compounds having an oxazolidone ring using a complex of aluminum halide catalyst |
| JPS5139665A (en) * | 1974-09-27 | 1976-04-02 | Mitsubishi Chem Ind | Okisazoridonrui no seizohoho |
| JPS51132231A (en) * | 1974-10-18 | 1976-11-17 | Hitachi Ltd | Heat curable adhesive |
| JPS51111296A (en) * | 1975-03-26 | 1976-10-01 | Hitachi Chem Co Ltd | Preparation of isocyanate epoxy prepolymer |
| US4386191A (en) * | 1981-10-08 | 1983-05-31 | Stauffer Chemical Company | Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom |
-
1985
- 1985-08-12 US US06/764,284 patent/US4614786A/en not_active Expired - Fee Related
-
1986
- 1986-07-24 EP EP86110217A patent/EP0217037A3/en not_active Withdrawn
- 1986-08-11 JP JP61187005A patent/JPS6289717A/en active Granted
- 1986-08-12 CA CA000515830A patent/CA1255036A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6289717A (en) | 1987-04-24 |
| US4614786A (en) | 1986-09-30 |
| EP0217037A2 (en) | 1987-04-08 |
| EP0217037A3 (en) | 1988-05-04 |
| JPH0455605B2 (en) | 1992-09-03 |
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