CA2039840A1 - Prepreg for high performance composite materials - Google Patents
Prepreg for high performance composite materialsInfo
- Publication number
- CA2039840A1 CA2039840A1 CA002039840A CA2039840A CA2039840A1 CA 2039840 A1 CA2039840 A1 CA 2039840A1 CA 002039840 A CA002039840 A CA 002039840A CA 2039840 A CA2039840 A CA 2039840A CA 2039840 A1 CA2039840 A1 CA 2039840A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- vinyl ester
- prepreg
- urethane resin
- ester urethane
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08J2375/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Springs (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
O.Z. 0050/41577 Abstract of the Disclosures Prepregs for high performance composite materials are based on oriented reinforcing fibers and a vinyl ester urethane resin comprising a reaction product of A) a polyisocyanate, with or without B1) a polyalcohol or B2) a polyamine and C) a hydroxyalkyl (meth)acrylate, and containing less than 2 % by weight of unsaturated monomers and in particular virtually no styrene.
Description
o.z. oo50/~;~9~34O
Prepreg for hiqh performance com~oqite materials The pre~ent invention relates to a prepreg for high performance compoqito materialq which i8 curable by a free radical reaction and is composed of an essentially monomer-freo vinyl ester urethane re~in and oriented reinfor~ing fiber3.
High performance compo~ite ma~erial~ are increa~-ingly used in the aircrsft and automotive vehicle indu~-tries. ~ighly stres~ed partq quch aq leaf springs are already being produced on an indu~trial ~cale from prepregs baqed sn epoxy ro~in~ and oriented glaR3 fiber bundles. Apart from thair high price, however, epoxy re4ins have the diQadvanta~e of comparatively long curing cycles; al~o, the cured compo~ite~ have an un~atis factorily high moi~ture regain.
It i~ an ob~ect of the pre~nt invention to provide a prepreg for high performancQ compo ite mater-ia7~ which i8 free of the disadvanta~es mentioned.
W~ hava found that this ob~ect is achieved by a prepreg compo~ed of oriented reinforcing fiber~ and essentially monomer-free vinyl e~ter ure~hane resins.
The present invention accor~ingly provides a prepreg for high performance composite material~ which i~
curable by a free radical re~ction, con~aining from 30 to 70 ~ by volum~ of oriented reinforcing fibax~ and from 70 to 30 ~ by volume of a vinyl ester urethans resin pre-pared by reacting ~) a polyi~ocyanate, with or without Bl) a diamin~ or B2) a dihydric alcohol and C) a hydroxyalkyl (meth)ac~.~late, in a weight ratio of As~Bl+B2) of from 100:0 to 100:30, preferably from 1nos5 to 100:15, the resin containing not more th~n l % by weight of free i~ocyanate groupY.
According to the invention, the vinyl e~ter urethane ;2 ~3~
Prepreg for hiqh performance com~oqite materials The pre~ent invention relates to a prepreg for high performance compoqito materialq which i8 curable by a free radical reaction and is composed of an essentially monomer-freo vinyl ester urethane re~in and oriented reinfor~ing fiber3.
High performance compo~ite ma~erial~ are increa~-ingly used in the aircrsft and automotive vehicle indu~-tries. ~ighly stres~ed partq quch aq leaf springs are already being produced on an indu~trial ~cale from prepregs baqed sn epoxy ro~in~ and oriented glaR3 fiber bundles. Apart from thair high price, however, epoxy re4ins have the diQadvanta~e of comparatively long curing cycles; al~o, the cured compo~ite~ have an un~atis factorily high moi~ture regain.
It i~ an ob~ect of the pre~nt invention to provide a prepreg for high performancQ compo ite mater-ia7~ which i8 free of the disadvanta~es mentioned.
W~ hava found that this ob~ect is achieved by a prepreg compo~ed of oriented reinforcing fiber~ and essentially monomer-free vinyl e~ter ure~hane resins.
The present invention accor~ingly provides a prepreg for high performance composite material~ which i~
curable by a free radical re~ction, con~aining from 30 to 70 ~ by volum~ of oriented reinforcing fibax~ and from 70 to 30 ~ by volume of a vinyl ester urethans resin pre-pared by reacting ~) a polyi~ocyanate, with or without Bl) a diamin~ or B2) a dihydric alcohol and C) a hydroxyalkyl (meth)ac~.~late, in a weight ratio of As~Bl+B2) of from 100:0 to 100:30, preferably from 1nos5 to 100:15, the resin containing not more th~n l % by weight of free i~ocyanate groupY.
According to the invention, the vinyl e~ter urethane ;2 ~3~
- 2 - o.z. 0050/41557 resin contains les~ than 2 % by weight of unsaturated monomer~.
Monomer-containing vinyl est~r urethanes have been known for a long tLme, for example from US-A-3 297 745 and US-A-3 772 404. US-A-4 390 662 describes mixture~ of un~aturated polyester~ with from O.5 to 70 % by weight of an acrylic urethane based on a long-chain polyesterpolyol or polyethexpolyol, which may also be monomer-free. Such re~ins are not suitable for producing hi~h performance compositz materials, since, owing to the high level of unsaturated polyester, the mechanical propertie~, in particular the heat resistance and the ~trength of the moldings, would be much too low.
US-A-4 131 602 describe~ the reaction of a triol or tetraol with a diisocyanate and a subsequent reaction with a hydroxyacrylate. The reaction product can be used as a radiation-curable coating agent.
VS-A-4 213 857 de~cribes the reaction products of bisphenol Atpolyester polyol with a polyi~ocyanate and a hydroxyl-terminated acrylic estQr. ThesQ vinyl ester urethanes, di~solved in copolymerizable ~olvents, are used a coating agents.
EPoA-64 809 describes a proces for producing a plastic moldin~ wherein a fluent solution of a poly-urethane-polyacrylate re~in in monomeric methyl methacry late i8 in~ected into a mold. Apart from the fact that thl~ mixtux~ contai.n~ large amount~ of a low-boiling monomer, it would not be suitable for Lmpregnating oriented reinforcing fibers and hence for producing high performance compo~ite materials on account of its low vis~osity.
DE-A-37 44 390 des~ribes compo~i~e material~
formed from reinforcing fiber3 and a modified vinyl ester urethane resLn which has a ~:umilar structure ~o the resin of the present invention. Where it differ~ significantly from the latter is that it is pres2n~ in solution in at least 15 % by weight of un~aturated monomsrs, preferably 2039~340 - 3 - o.z. 0050/41557 instyrene. Such low-vi~cosity resins are highly suitable for Lmpre~nating the loose fiber mat~ which are preferred as reinforcing fiber~ in said DE-A-37 44 390. For Lmpreg-nating oriented reinforcing fiber~ of the type required S in prepregs for high performance composite materials and for the further proces~ing of the prepreg, however, their vi~co~ity would be much too low. Moreover, the styrene, because of its high vapor pressure, would pra~ent a problem in the processing of the prepreg by the autoclave method.
The following remarks concern tha starting material:
Reinforcing fiber Suitable reinforcing fibers are customary inor-ganic or organic fibers, preferably those made of gla~R,carbon or aromatic polyamide. The e~Yential a~pect is that the fiber~ are oriented. Fiber m~t~ are thuR not suitable. Preference i~ given to laid fiber~, in par-ticular unidir~ctionally oriant0d gla88 fibers, and to woven fibars. The prepregs of the present invention contain ~rom 30 to 70, preferably from 50 to 60, % ~y volume of reinforcing fiber3.
IRocyanato~
To prepare tho vinyl e.~ter urethane resins for the purpos~s o~ the present in~an~ion it i8 possibl~ to u8e any ~nown aliphatic, cycoaliphatic or aromatic polyisocyanAte havin~ at least 2 isocyanate groups per molaculeO E~camples of ~uitable isocyanate~ are:
Monomer-containing vinyl est~r urethanes have been known for a long tLme, for example from US-A-3 297 745 and US-A-3 772 404. US-A-4 390 662 describes mixture~ of un~aturated polyester~ with from O.5 to 70 % by weight of an acrylic urethane based on a long-chain polyesterpolyol or polyethexpolyol, which may also be monomer-free. Such re~ins are not suitable for producing hi~h performance compositz materials, since, owing to the high level of unsaturated polyester, the mechanical propertie~, in particular the heat resistance and the ~trength of the moldings, would be much too low.
US-A-4 131 602 describe~ the reaction of a triol or tetraol with a diisocyanate and a subsequent reaction with a hydroxyacrylate. The reaction product can be used as a radiation-curable coating agent.
VS-A-4 213 857 de~cribes the reaction products of bisphenol Atpolyester polyol with a polyi~ocyanate and a hydroxyl-terminated acrylic estQr. ThesQ vinyl ester urethanes, di~solved in copolymerizable ~olvents, are used a coating agents.
EPoA-64 809 describes a proces for producing a plastic moldin~ wherein a fluent solution of a poly-urethane-polyacrylate re~in in monomeric methyl methacry late i8 in~ected into a mold. Apart from the fact that thl~ mixtux~ contai.n~ large amount~ of a low-boiling monomer, it would not be suitable for Lmpregnating oriented reinforcing fibers and hence for producing high performance compo~ite materials on account of its low vis~osity.
DE-A-37 44 390 des~ribes compo~i~e material~
formed from reinforcing fiber3 and a modified vinyl ester urethane resLn which has a ~:umilar structure ~o the resin of the present invention. Where it differ~ significantly from the latter is that it is pres2n~ in solution in at least 15 % by weight of un~aturated monomsrs, preferably 2039~340 - 3 - o.z. 0050/41557 instyrene. Such low-vi~cosity resins are highly suitable for Lmpre~nating the loose fiber mat~ which are preferred as reinforcing fiber~ in said DE-A-37 44 390. For Lmpreg-nating oriented reinforcing fiber~ of the type required S in prepregs for high performance composite materials and for the further proces~ing of the prepreg, however, their vi~co~ity would be much too low. Moreover, the styrene, because of its high vapor pressure, would pra~ent a problem in the processing of the prepreg by the autoclave method.
The following remarks concern tha starting material:
Reinforcing fiber Suitable reinforcing fibers are customary inor-ganic or organic fibers, preferably those made of gla~R,carbon or aromatic polyamide. The e~Yential a~pect is that the fiber~ are oriented. Fiber m~t~ are thuR not suitable. Preference i~ given to laid fiber~, in par-ticular unidir~ctionally oriant0d gla88 fibers, and to woven fibars. The prepregs of the present invention contain ~rom 30 to 70, preferably from 50 to 60, % ~y volume of reinforcing fiber3.
IRocyanato~
To prepare tho vinyl e.~ter urethane resins for the purpos~s o~ the present in~an~ion it i8 possibl~ to u8e any ~nown aliphatic, cycoaliphatic or aromatic polyisocyanAte havin~ at least 2 isocyanate groups per molaculeO E~camples of ~uitable isocyanate~ are:
4,4-diphenyLmethan~ diisocyanate (MDI), hexamethylene dii~ocyanate (HDI), trimethylhexyl diisocyanata ( TMDI ), cyclohexyl diisocyanate, dicyclopenta~ienedimethylena diisocyanate, diisocyanatodiphenyl ether, diiqocyanato-naphthalene, diphenylmethane diisocyanate and diisocyana-totoluene with t.heir isomer mixture~, isophorone dii30cyan~te (IPDI), dicyclohexyl diisocyanate, poly-phenylenepolymethylene polyisocyanates ~crude MDI);
triisocyanatocyclohexane, trii~ocyanatotoluene, ;~39~40 - 4 - O.Z. 0050/41557 triisocyanatonaphthalene, triisiocyanatobiphenyl, tri-isocyanatotrLmethylbenzenQ, trii~iocyanotodiphenylmethane, triisocyanatomethyldiphenylmethane, triisocyanatotri-phenylmethane, triiqiocyanatodiphenyl ether, tetraiso-cyanatodiphenyl sulfide; urethane-containing prepolymeric polyisiocyanates siuch a~ the reaction product of trimethy-lolpropane and diiqiocyan~otoluene; trLmerized polyiso-cyanate~i which contain isocyanurate groups and are hased for example on HDI t diphenylmethane diisiocyanatQ and isophoronQ diisiscyanate; prepolymeric polyisocyanateq prepared by reaction of polyisiocyanate~i with A deficiency of polyepoxide~i in th~ pre~3ienca of suitable cataly3tsi;
polyisiocyanatesi which by prereaction of ~iome of the NCO
groupsi contain earbodiLmide and urethoneLminQ units; and also prepolymersi which contain not only NCO group~ but urethdione unitq.
Preferred isiQcyanates are 4,4'-diphenylmethane diisocyanate and the isom~r mixture of 2,2'- a~d 4,4'-diphenylmethane diisocyanate.
Diamines Suitable diamines includ~ not only aliphatic amine~i but al~io aromatic amine~i. Example~ are: ethylene-diamine, diethylenetriamine, bi~(4-aminocyclohexyl)meth-ane, diaminodiphenylmethane and diaminodiphenyl ~3iulfone.
Particularly suitable aminas are long-chain amines having molecular weights of from 150 to 5000. Thsy include ether diam~ne~ ~3iuch 28 4,7-dioxadecRne-1,10diamine and com-pound~ of the general formula H2N (C3H60)m-C3H6-NH2, where m i9 from 2 to 80, or cempounds of the general formula H 2N-C 3H6 ~0- [ ( CH 2 ) 4] n -C 3H6 -NH 2, where n isi from 5 to 80; alsio the aminobenzoic estersii and ~039l~4~) - 5 - O.Z. OOS0/41557 anthranilic e~ter~ of diol~ ~uch a~ ethylenQ glycol, propylene glycol, polyethylene glycol, polypropylene glycol, p~lybutadiene glycol, polycaprolactone glycol or polytetramethylene ether glycol. The particularly pre-ferred aminobenzoic est2r~ of polytetramQthylene etherglycol have the following structure:
H2~ C02--C4H90--r (CH2) 40] -C4~18-02C~ NH2 where p i8 from S to 80.
Dihydric alcohol~
E~ample~ of dihydric alcohols which are quitable for reaction with i~ocyanate~ are: aliphatic diol~ or polyetherol~, preferably those having a molecular weight of le~ than 750, in particular le~ than 600, such a3 1,2 ethanediol, 1,2-propanediol, 1,4-butanediol, dipropy-lene glycol, neopentylglycol, and alAo polyethylene glycol and polypropylene glycol, or alicyclic diol~, such a hydrogsnated bisphenol A, cyclohexanediol, cyclo-hexanedimethanol and tricyclohexanedLmethanol, also phenols such as bisphenol A or re~orcinol, and also alko~ylated derivatives of bi~phenol~ such a~
bisphenol A, bisphenol S or bi3phenol P. In principle it i~ al~o possible to reaet the isocyanate~ with aminol~
quch as ethanolamine, propanolamine, diethanolamine, triethanol~mine and aminophanol~. Preferance i~ given to dipropylsne glycol with or without polypropylene glycol.
Hydroxyalkyl (meth)acrylates To incorporate the terminal double bonds into vinyl ester urethane, hydroxyalkyl (meth)acrylateR are reacted with the i~ocyanate cempounds prepared from A, B1 and B2. Hydroxyalkyl (meth)ac~rrlate~ ~r~ de~cribed by the following general formulas C H 2=C--C0 2--R --OH
2()39~
triisocyanatocyclohexane, trii~ocyanatotoluene, ;~39~40 - 4 - O.Z. 0050/41557 triisocyanatonaphthalene, triisiocyanatobiphenyl, tri-isocyanatotrLmethylbenzenQ, trii~iocyanotodiphenylmethane, triisocyanatomethyldiphenylmethane, triisocyanatotri-phenylmethane, triiqiocyanatodiphenyl ether, tetraiso-cyanatodiphenyl sulfide; urethane-containing prepolymeric polyisiocyanates siuch a~ the reaction product of trimethy-lolpropane and diiqiocyan~otoluene; trLmerized polyiso-cyanate~i which contain isocyanurate groups and are hased for example on HDI t diphenylmethane diisiocyanatQ and isophoronQ diisiscyanate; prepolymeric polyisocyanateq prepared by reaction of polyisiocyanate~i with A deficiency of polyepoxide~i in th~ pre~3ienca of suitable cataly3tsi;
polyisiocyanatesi which by prereaction of ~iome of the NCO
groupsi contain earbodiLmide and urethoneLminQ units; and also prepolymersi which contain not only NCO group~ but urethdione unitq.
Preferred isiQcyanates are 4,4'-diphenylmethane diisocyanate and the isom~r mixture of 2,2'- a~d 4,4'-diphenylmethane diisocyanate.
Diamines Suitable diamines includ~ not only aliphatic amine~i but al~io aromatic amine~i. Example~ are: ethylene-diamine, diethylenetriamine, bi~(4-aminocyclohexyl)meth-ane, diaminodiphenylmethane and diaminodiphenyl ~3iulfone.
Particularly suitable aminas are long-chain amines having molecular weights of from 150 to 5000. Thsy include ether diam~ne~ ~3iuch 28 4,7-dioxadecRne-1,10diamine and com-pound~ of the general formula H2N (C3H60)m-C3H6-NH2, where m i9 from 2 to 80, or cempounds of the general formula H 2N-C 3H6 ~0- [ ( CH 2 ) 4] n -C 3H6 -NH 2, where n isi from 5 to 80; alsio the aminobenzoic estersii and ~039l~4~) - 5 - O.Z. OOS0/41557 anthranilic e~ter~ of diol~ ~uch a~ ethylenQ glycol, propylene glycol, polyethylene glycol, polypropylene glycol, p~lybutadiene glycol, polycaprolactone glycol or polytetramethylene ether glycol. The particularly pre-ferred aminobenzoic est2r~ of polytetramQthylene etherglycol have the following structure:
H2~ C02--C4H90--r (CH2) 40] -C4~18-02C~ NH2 where p i8 from S to 80.
Dihydric alcohol~
E~ample~ of dihydric alcohols which are quitable for reaction with i~ocyanate~ are: aliphatic diol~ or polyetherol~, preferably those having a molecular weight of le~ than 750, in particular le~ than 600, such a3 1,2 ethanediol, 1,2-propanediol, 1,4-butanediol, dipropy-lene glycol, neopentylglycol, and alAo polyethylene glycol and polypropylene glycol, or alicyclic diol~, such a hydrogsnated bisphenol A, cyclohexanediol, cyclo-hexanedimethanol and tricyclohexanedLmethanol, also phenols such as bisphenol A or re~orcinol, and also alko~ylated derivatives of bi~phenol~ such a~
bisphenol A, bisphenol S or bi3phenol P. In principle it i~ al~o possible to reaet the isocyanate~ with aminol~
quch as ethanolamine, propanolamine, diethanolamine, triethanol~mine and aminophanol~. Preferance i~ given to dipropylsne glycol with or without polypropylene glycol.
Hydroxyalkyl (meth)acrylates To incorporate the terminal double bonds into vinyl ester urethane, hydroxyalkyl (meth)acrylateR are reacted with the i~ocyanate cempounds prepared from A, B1 and B2. Hydroxyalkyl (meth)ac~rrlate~ ~r~ de~cribed by the following general formulas C H 2=C--C0 2--R --OH
2()39~
- 6 - o.z. 0050/41557 where R i~ hydrogen or methyl and R' is alkylene of 2 or 3 carbon atom~. Hydroxyalkyl (meth)acrylates are prepared by reacting (meth)acrylic acid with alkylene oxide~ ~uch a~ ~thylene oxide or propylene oxide. Suitable hydroxyalkyl (meth)acrylates for th~ purpose~ of the present invention also include glycerol (dLmeth)acrylates, trLmethylolpropane (dimeth)-acrylate~ and pentaerythritol (trLmeth)acrylates, with hydroxypropyl (meth)acrylate and hydroxyethyl (meth)-acrylate being preferred.Monomers According to the present invention, the vinyl ester urethane resin contains less than 2, preferably le~ than l, % by weight of monomer~ having a boiling point above 200C (at 1013 mbar). These may be added for specifically adjusting the vi~cosity, in which ca~e the preference i~ for di(meth)acrylate~ of diols or poly-etherol~, low molecular weight maleimide~ such as N-phenylmaleLmide/ N-alkylmaleimides and N-cyclohexyl-maleLmide~, and diallyl phthalate. The e~sential require-ment i3 that the resin shall be vlrtually free of monomer~ having a lower boiling point, in particular that the re~in~ ~hall be free of styrene.
The vinyl e~ter urethane re~in3 used according to the present invention ~hould have a comparatively high vi3cosity. The melt vi8c08ity, measured at 100C using an Epprecht plate/cone vi~cometer, should preferably be above 50 mPa~, in particular within the range from ~00 to 2500 ~Pas. I~ the vi co~ity i3 too low, tho re~in will flow out of the prepreg at room temperature; if the viscosity i~ too high, there is a danger of fiber~
breaking as thay are being impregnated. The mo~t 4uitable viscosLty can be ~et throush appropriate choica of the molecular weight of the re~in (ad~u~table via the diols or diamine4) or by adding th~rmoplastic~ or rubbers which may carry reactive groupC (for example COOH, OH or NH2 group~). The vi~cosity can al~o be influenced by the ~9~o - 7 - o.Z. 0050~41557 addition of small amounts of monomer~.
To speed up the reactions of the isocyanates ~ith the alcohol and amino compound~ i~ is possible to use suitable cat~lyst~ as known from polyurethane chemistry.
S They include for exampla tertiary amines such as 1,2-dLmethylLmidazole, diazabicyclooctane, diazabi-cyclononane, triethylenediamine, metal salts such as lead octoate, tin octoate or dibutyltin dilaurate and also mixtures of tertiary amine~ and metal salts. The3e catalyst~ are cu~tomarily added in amoun~ of from 0.05 to 2 ~ by weight, ba~ed on A + B + C.
Pr~mature gelation of the reaction mixture can be prevented by the addition of customary inhibitors, eg.
phenothiazine, hydroquinone, dimethylhydroquinone, trLmethylhydroquinons~ tertbutylhydroquinone, hydro-quinone monomethyl ether, tert-butylpyrocatechol, triphenyl phosphite or p-benzoquinone. The inhibitor~ are added in amounts of from 0.01 to 2 % by weight, based on A + B ~ C.
To prepare tho modified vinyl ester urethane re~in~ there aro various options. Pir~t, the i~acyanate A
can b~ prereacted with a portion of ~he hydroxyalkyl (meth)acrylate C in a molar ratio of about 1:0.5-1:1.5 and then with the polyhydric alcohol B2 and/or the poly-amine Bl, theraaftar the free NCO groups are reacted with the remaining hydroxyalkyl (meth)acrylate. Secondly, by mixing the components A, Bl and any ~2 in a ratio of A:(Bl+B2) of from 100:0 to 100:30 and re~cting at 40-110C before adding the amount of hydroxyalkyl (meth)-acrylate C required for ~aturating the freu isocyanate groups. Thirdly, by reacting the component~ A, ~1, B2 and C together in a ono-pot reaction to glve the vinyl ester urethane resin. Any exce~ polyisocyanate present reacts with thQ hydroxyalkyl (me~h)acrylat6 to give a low molecular w~ight vinyl e~ter urothane which may be utilized for ad~usting the ~iSc08ity of the re~in. The product obtained at all times i8 a mixture of 2~)35~8~
The vinyl e~ter urethane re~in3 used according to the present invention ~hould have a comparatively high vi3cosity. The melt vi8c08ity, measured at 100C using an Epprecht plate/cone vi~cometer, should preferably be above 50 mPa~, in particular within the range from ~00 to 2500 ~Pas. I~ the vi co~ity i3 too low, tho re~in will flow out of the prepreg at room temperature; if the viscosity i~ too high, there is a danger of fiber~
breaking as thay are being impregnated. The mo~t 4uitable viscosLty can be ~et throush appropriate choica of the molecular weight of the re~in (ad~u~table via the diols or diamine4) or by adding th~rmoplastic~ or rubbers which may carry reactive groupC (for example COOH, OH or NH2 group~). The vi~cosity can al~o be influenced by the ~9~o - 7 - o.Z. 0050~41557 addition of small amounts of monomer~.
To speed up the reactions of the isocyanates ~ith the alcohol and amino compound~ i~ is possible to use suitable cat~lyst~ as known from polyurethane chemistry.
S They include for exampla tertiary amines such as 1,2-dLmethylLmidazole, diazabicyclooctane, diazabi-cyclononane, triethylenediamine, metal salts such as lead octoate, tin octoate or dibutyltin dilaurate and also mixtures of tertiary amine~ and metal salts. The3e catalyst~ are cu~tomarily added in amoun~ of from 0.05 to 2 ~ by weight, ba~ed on A + B + C.
Pr~mature gelation of the reaction mixture can be prevented by the addition of customary inhibitors, eg.
phenothiazine, hydroquinone, dimethylhydroquinone, trLmethylhydroquinons~ tertbutylhydroquinone, hydro-quinone monomethyl ether, tert-butylpyrocatechol, triphenyl phosphite or p-benzoquinone. The inhibitor~ are added in amounts of from 0.01 to 2 % by weight, based on A + B ~ C.
To prepare tho modified vinyl ester urethane re~in~ there aro various options. Pir~t, the i~acyanate A
can b~ prereacted with a portion of ~he hydroxyalkyl (meth)acrylate C in a molar ratio of about 1:0.5-1:1.5 and then with the polyhydric alcohol B2 and/or the poly-amine Bl, theraaftar the free NCO groups are reacted with the remaining hydroxyalkyl (meth)acrylate. Secondly, by mixing the components A, Bl and any ~2 in a ratio of A:(Bl+B2) of from 100:0 to 100:30 and re~cting at 40-110C before adding the amount of hydroxyalkyl (meth)-acrylate C required for ~aturating the freu isocyanate groups. Thirdly, by reacting the component~ A, ~1, B2 and C together in a ono-pot reaction to glve the vinyl ester urethane resin. Any exce~ polyisocyanate present reacts with thQ hydroxyalkyl (me~h)acrylat6 to give a low molecular w~ight vinyl e~ter urothane which may be utilized for ad~usting the ~iSc08ity of the re~in. The product obtained at all times i8 a mixture of 2~)35~8~
- 8 o.Z~ 0050/41557 prepolymeric vinyle~terurethanes which differ in chain length and molecular weight. In principle it is also possible ~o U5e the sLmple reaction product of 2 mol of hydro~yalkyl (meth)acrylate with 1 mol of diosocyanate.
S The vinyl ester urethane resin may be admixed with amounts of from 2 to 20 % of it~ weight of other curable resins, such as vinyl ester, bismaleLmide or epoxy re ins. To Lmprove it~ toughne~ the vinyl eqter urethane resin may contain from 2 to 20 % of i~ weight of a thermoplastic, such a~ polyamide, polye~ter or polyether sulfone, or of a rubber.
Tha vinyl ester urethane resin~ are combined with reinforcing fiber~ by the preprag technique. This tech-nique i~ described for example in US-A-3 784 433. First a vinyl ester urethane re3in film i~ prepared, preferably with a sheet weight of from 10 to 400 g-m~2, and ~he a~sembly of reinforcing fiber i8 laid on top of thi~
film, po~sibly with another re~in film on top. The layers are calendsred together at 50-150~C and 1-10 bar to give a prepreg.
These prepregq can be draped on top of one another in a plurality of plieR and then molded ~ogether and ~ub~ected to fres radical curing in a conventional manner. To this end, the prepregs are cut to si2e and draped on top of one another in a parallel arrangement or oriented at various angles. The curing then takes place either in an autoclave at from 2 to 10 bar or in a pre~s at from 10 to 100 bar. In either case the temperature is within the range from 80 to 200C.
To cure the vinyl ester urethane resins it i5 possible to U~Q customary polymerlzation initiators, which are added to the resin in amounts of from 0.1 to 10 % by weight, preferably from 0.5 to 3 % by weight.
Suitable free radical initiators are for example: benzoyl peroxid~, tert-butyl peroctoate, tert-butyl per~
benzoate, tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di(4-methylbenzoyl)peroxide, ~039~34~) - 9 _ o.z. 0050/41557 di(tert-hutyl)peroxide and orqanic compound~ having a labile carbon-carbon bond. If cu~tomary photoinitiators, eg. henzoin ether~, benzil ketals or acylphosphine compound~, are u~ed, ths curing may alternatively be carri~d out by irradiation wLth light of wavelength 200-50 nm.
The prepregs of the pre~ent invention can be used to produce high performance composite materials, for example aircraft part~, eg. aileron~ and fuselage shells, automobile part~, machine parts or sports article~, eg.
tennis rackets or fi~hing rod3~
The present invention further provides high performance compoxit~ materialc containing frsm 30 to 70 % ~y volume of oriented glass fiber and from 70 ~o 30 % by ~olume of a cured vinyl e~ter urethane resin which contain~ virtually no copolymerized ~tyrene units, which are defined by the following propertieY: an inter-laminar hear ~trength ILS, maasured in accordance with Sacma S~andard SR~ 4-88, of greater than 90, preferably greater than 100 [MPa], a 90 ten9il2 strength, measured in accordanc with Sacma Standard SR~ 8~88, of greater than 50, preforably greater than 70 [MPa], and a glass transition temperature Tg of more than 130C, preferably more than l50~C.
E~AMPLES
A. Preparation of vinyl estar urethane resin 1. 300 g of the isomer m$xture of diphenylmethane diisocyanate ara admixed with 1 ml of dibutyltin dilau~ate, and 157 g of hydroxypropyl methacrylate are added dropwi~e a~ 40C. ~hen 15 g of dipropylene glycol are added, the remaining isocyanate groups are reacted with a further 157 g of hydroxypropyl methacrylata, and the reaction mixture i8 ~u,bsequently stirred at 80C
until tha residual isocyanate content ha~ dropped to belsw 0.1 %, at which point 0.61 g of dicumyl peroxide and 200 ppm of phenolic inhibLtor are s~irred into the resin (visco~ity 390 mPah at 100C).
~035~840 - .L0 - O.Z. 0050/41557 2. 325 g of a prepolymeric diisocyanate based on 282 g of 4,4'-diphenylmethane diisocyana~a, 27.1 g of dipro-pylene glycol and 15.9 g of polypropylene glycol (MW 450) are admixed with 1 ml of dibutyltin dilaurate ~nd reacted at 40C with 260 g of hydroxypropyl methacrylate. The mixture is then stirred at 90C for 1 h, catalyzed with 0.58 g of dicumyl peroxide and inhibited with 200 ppm of a phenol. The vi~co~ity of the re~in at 100C is 1700 mPas.
3. 2,530 g of the i~omer mixture of diphenylmethane diisocyanate are admixed with 2 ml of dibutyltin diluarate and reacted at 40C with 940 g of bis(para-aminobenzoic ester)polytetrahydrofuran 650. Thereafter 2,760 g of hydroxypropyl (meth)acrylate are added at 50C, and the mixture i~ heated to 70C and stirred at that temperature for 1 hour. The re~in i5 admixed with 400 ppm of dimethylhdyroquinone and 31.3 g of dicumyl peroxide. The resin has a melt viscosity (100C) of 480 mPa~.
4. 3,006 g of the i~omer mixture of diphenylme~hane diixocyanate are admixad with 195 g of a rubber based on acrylate (Paraloid E~L 2600) and 3.5 ml of dibutyotin dilaurate and reacted at 40-50~C wi~h 1,572 g of hydroxy-propyl (meth)acrylate. Then 151 g of dipropylena glycol ar~ added at thst temperature, followed by a further 1,572 ~ of h~droxypropyl (meth)acrylate. This is in turn followad by 3 ml of dibutyltin dilaurate, 6.3 g of phenothiazine and 6.3 g of triphenyl phosphite, heating to 80-C and stirring at that temperature for 1 hour. The mixtur~ i~ then cooled down to 70 and admixed with 63 g of dicumyl peroxido,The re~in has a vi~cosity of 340 mPas (cone/plate viscosity at 100C).
Hl. Prepar~tion of prepreg with gla~s fibres The vinyl ester ure~hane resins are first applied with a laboratory coater to ~iliconized paper in a film w~igh~ of 140 g.m~2 by the method of contrarotation and the U8Q of a nip. The film i8 then covered with a sheet 2;0~989~
~ O.Z. 0050/41557 of polyethylenQ and wound up.
Parallel gla~s fiber roving~ (PPG 1062-247) are then pres~ed in a sheet weight of 560 g m 2 into the re~in film by the two-film technique using three calender~ at 60-140C and 1-8 bar. In the course of the calendering the resin film become attached to the laid rovings. The prepreg i~ then covered with ~iliconized paper and a ~heet of polyethylene, rollad up and ~tored. The shee~
weight of the prepreg is 840 g m~2.
B2. Prepregs with carbon fiber~
~he resin film (sheet weight 70 g m~2) i~ molded by the ingle-film technique with parallel carbon fiber roving~ (Celion G 30-S00) having a sheet waight of 140 g m~2. The prepreg ~heet weight i8 210 g-m~2 and the - 15 re~in content i~ 33 % by weight.
C. Production of a composite material The prepreg~ are trlmmed in size to 30x3G cm, and 6 ~uch cut~ are then draped on top of one another unidir-ectionally and cured in an autoclave. The prassure i~
6 bar, and the tempera~ure i~ rai~ed from 30 to 190C in the course of 8 h.
The laminate havo the properties indicated in the table. For comp~rison the table al~o include~ a laminat~ based on a convention~l epoxy resin (mixture of tetraglycidyldiaminodiFhenylm~thane + bisphenol A epoxide + novol2k epoxide + dicyandiamide).
TABLE
Resin Al A2 A3 A4 Epoxy Al F1bers B1 B1 B1 B1 B1 s2 . _ ILS (dry, 23C) [MPa] 119 11696 108 34 116 Tensile ~trength [~IPa] 84 79 76 - 75 Tg [ C] 181 1132175 186185 178
S The vinyl ester urethane resin may be admixed with amounts of from 2 to 20 % of it~ weight of other curable resins, such as vinyl ester, bismaleLmide or epoxy re ins. To Lmprove it~ toughne~ the vinyl eqter urethane resin may contain from 2 to 20 % of i~ weight of a thermoplastic, such a~ polyamide, polye~ter or polyether sulfone, or of a rubber.
Tha vinyl ester urethane resin~ are combined with reinforcing fiber~ by the preprag technique. This tech-nique i~ described for example in US-A-3 784 433. First a vinyl ester urethane re3in film i~ prepared, preferably with a sheet weight of from 10 to 400 g-m~2, and ~he a~sembly of reinforcing fiber i8 laid on top of thi~
film, po~sibly with another re~in film on top. The layers are calendsred together at 50-150~C and 1-10 bar to give a prepreg.
These prepregq can be draped on top of one another in a plurality of plieR and then molded ~ogether and ~ub~ected to fres radical curing in a conventional manner. To this end, the prepregs are cut to si2e and draped on top of one another in a parallel arrangement or oriented at various angles. The curing then takes place either in an autoclave at from 2 to 10 bar or in a pre~s at from 10 to 100 bar. In either case the temperature is within the range from 80 to 200C.
To cure the vinyl ester urethane resins it i5 possible to U~Q customary polymerlzation initiators, which are added to the resin in amounts of from 0.1 to 10 % by weight, preferably from 0.5 to 3 % by weight.
Suitable free radical initiators are for example: benzoyl peroxid~, tert-butyl peroctoate, tert-butyl per~
benzoate, tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di(4-methylbenzoyl)peroxide, ~039~34~) - 9 _ o.z. 0050/41557 di(tert-hutyl)peroxide and orqanic compound~ having a labile carbon-carbon bond. If cu~tomary photoinitiators, eg. henzoin ether~, benzil ketals or acylphosphine compound~, are u~ed, ths curing may alternatively be carri~d out by irradiation wLth light of wavelength 200-50 nm.
The prepregs of the pre~ent invention can be used to produce high performance composite materials, for example aircraft part~, eg. aileron~ and fuselage shells, automobile part~, machine parts or sports article~, eg.
tennis rackets or fi~hing rod3~
The present invention further provides high performance compoxit~ materialc containing frsm 30 to 70 % ~y volume of oriented glass fiber and from 70 ~o 30 % by ~olume of a cured vinyl e~ter urethane resin which contain~ virtually no copolymerized ~tyrene units, which are defined by the following propertieY: an inter-laminar hear ~trength ILS, maasured in accordance with Sacma S~andard SR~ 4-88, of greater than 90, preferably greater than 100 [MPa], a 90 ten9il2 strength, measured in accordanc with Sacma Standard SR~ 8~88, of greater than 50, preforably greater than 70 [MPa], and a glass transition temperature Tg of more than 130C, preferably more than l50~C.
E~AMPLES
A. Preparation of vinyl estar urethane resin 1. 300 g of the isomer m$xture of diphenylmethane diisocyanate ara admixed with 1 ml of dibutyltin dilau~ate, and 157 g of hydroxypropyl methacrylate are added dropwi~e a~ 40C. ~hen 15 g of dipropylene glycol are added, the remaining isocyanate groups are reacted with a further 157 g of hydroxypropyl methacrylata, and the reaction mixture i8 ~u,bsequently stirred at 80C
until tha residual isocyanate content ha~ dropped to belsw 0.1 %, at which point 0.61 g of dicumyl peroxide and 200 ppm of phenolic inhibLtor are s~irred into the resin (visco~ity 390 mPah at 100C).
~035~840 - .L0 - O.Z. 0050/41557 2. 325 g of a prepolymeric diisocyanate based on 282 g of 4,4'-diphenylmethane diisocyana~a, 27.1 g of dipro-pylene glycol and 15.9 g of polypropylene glycol (MW 450) are admixed with 1 ml of dibutyltin dilaurate ~nd reacted at 40C with 260 g of hydroxypropyl methacrylate. The mixture is then stirred at 90C for 1 h, catalyzed with 0.58 g of dicumyl peroxide and inhibited with 200 ppm of a phenol. The vi~co~ity of the re~in at 100C is 1700 mPas.
3. 2,530 g of the i~omer mixture of diphenylmethane diisocyanate are admixed with 2 ml of dibutyltin diluarate and reacted at 40C with 940 g of bis(para-aminobenzoic ester)polytetrahydrofuran 650. Thereafter 2,760 g of hydroxypropyl (meth)acrylate are added at 50C, and the mixture i~ heated to 70C and stirred at that temperature for 1 hour. The re~in i5 admixed with 400 ppm of dimethylhdyroquinone and 31.3 g of dicumyl peroxide. The resin has a melt viscosity (100C) of 480 mPa~.
4. 3,006 g of the i~omer mixture of diphenylme~hane diixocyanate are admixad with 195 g of a rubber based on acrylate (Paraloid E~L 2600) and 3.5 ml of dibutyotin dilaurate and reacted at 40-50~C wi~h 1,572 g of hydroxy-propyl (meth)acrylate. Then 151 g of dipropylena glycol ar~ added at thst temperature, followed by a further 1,572 ~ of h~droxypropyl (meth)acrylate. This is in turn followad by 3 ml of dibutyltin dilaurate, 6.3 g of phenothiazine and 6.3 g of triphenyl phosphite, heating to 80-C and stirring at that temperature for 1 hour. The mixtur~ i~ then cooled down to 70 and admixed with 63 g of dicumyl peroxido,The re~in has a vi~cosity of 340 mPas (cone/plate viscosity at 100C).
Hl. Prepar~tion of prepreg with gla~s fibres The vinyl ester ure~hane resins are first applied with a laboratory coater to ~iliconized paper in a film w~igh~ of 140 g.m~2 by the method of contrarotation and the U8Q of a nip. The film i8 then covered with a sheet 2;0~989~
~ O.Z. 0050/41557 of polyethylenQ and wound up.
Parallel gla~s fiber roving~ (PPG 1062-247) are then pres~ed in a sheet weight of 560 g m 2 into the re~in film by the two-film technique using three calender~ at 60-140C and 1-8 bar. In the course of the calendering the resin film become attached to the laid rovings. The prepreg i~ then covered with ~iliconized paper and a ~heet of polyethylene, rollad up and ~tored. The shee~
weight of the prepreg is 840 g m~2.
B2. Prepregs with carbon fiber~
~he resin film (sheet weight 70 g m~2) i~ molded by the ingle-film technique with parallel carbon fiber roving~ (Celion G 30-S00) having a sheet waight of 140 g m~2. The prepreg ~heet weight i8 210 g-m~2 and the - 15 re~in content i~ 33 % by weight.
C. Production of a composite material The prepreg~ are trlmmed in size to 30x3G cm, and 6 ~uch cut~ are then draped on top of one another unidir-ectionally and cured in an autoclave. The prassure i~
6 bar, and the tempera~ure i~ rai~ed from 30 to 190C in the course of 8 h.
The laminate havo the properties indicated in the table. For comp~rison the table al~o include~ a laminat~ based on a convention~l epoxy resin (mixture of tetraglycidyldiaminodiFhenylm~thane + bisphenol A epoxide + novol2k epoxide + dicyandiamide).
TABLE
Resin Al A2 A3 A4 Epoxy Al F1bers B1 B1 B1 B1 B1 s2 . _ ILS (dry, 23C) [MPa] 119 11696 108 34 116 Tensile ~trength [~IPa] 84 79 76 - 75 Tg [ C] 181 1132175 186185 178
Claims (4)
1. A prepreg for high performance composite mater-ials which is curable by a free radical reaction, con-taining from 30 to 70 % by volume of oriented reinforcing fibers and from 70 to 30 % by volume of a vinyl ester urethane resin prepared by reacting A) a polyisocyanate, with or without B1) a diamine or B2) a dihydric alcohol and C) a hydroxyalkyl (meth)acrylate, in a weight ratio of A:(B1+B2) of from 100:0 to 100:30, the resin containing not more than l % by weight of free isocyanate groups wherein the vinyl ester urethane resin contains less than 2 % by weight of unsaturated monomers having a boiling point above 200°C an no monomers having a lower boiling point.
2. A prepreg as claimed in claim 1, wherein the vinyl ester urethane resin contains from 2 to 20 % by weight, based on its weight, of a curable resin, of a thermoplastic or of a rubber in admixture.
3. A prepreg as claimed in claim 1, wherein the vinyl ester urethane resin contains from 0.1 to 10 % by weight of a peroxido initiator.
4. A high performance composite material containing from 30 to 70 % by volume of unidirectionally oriented glass fibers and from 70 to 30 % by volume of a cured vinyl ester urethane resin which contains groups (where n is 2 or 3 and R is H or CH3) but no groups, - 13 - O.Z. 0050/41577 defined by the following properties:
interlaminar shear strength (ILS) > 90 [MPa]
90° tensile strength > 50 [MPa]
glass transition temperature > 130°C.
interlaminar shear strength (ILS) > 90 [MPa]
90° tensile strength > 50 [MPa]
glass transition temperature > 130°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4012946A DE4012946A1 (en) | 1990-04-24 | 1990-04-24 | PREPREG FOR HIGH-PERFORMANCE COMPOSITES |
| DEP4012946.2 | 1990-04-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2039840A1 true CA2039840A1 (en) | 1991-10-25 |
Family
ID=6404925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002039840A Abandoned CA2039840A1 (en) | 1990-04-24 | 1991-04-15 | Prepreg for high performance composite materials |
Country Status (4)
| Country | Link |
|---|---|
| EP (2) | EP0458028A1 (en) |
| JP (2) | JPH04227656A (en) |
| CA (1) | CA2039840A1 (en) |
| DE (1) | DE4012946A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2513207B1 (en) | 2009-12-14 | 2017-05-03 | Gurit (UK) Ltd. | Prepregs for manufacturing composite materials |
| US20200385539A1 (en) * | 2017-09-27 | 2020-12-10 | Dic Corporation | Prepreg resin composition, prepreg and molded article |
| US11198281B2 (en) | 2016-09-26 | 2021-12-14 | Mitsubishi Chemical Corporation | Laminated film for fiber adhesion and/or fiber sheet surface protection and thermosetting composition for fiber adhesion and/or fiber sheet surface protection |
| CN114539718A (en) * | 2022-02-28 | 2022-05-27 | 山东莱蔚特复合材料有限责任公司 | Preparation method of mould pressing composite material plate spring |
| US11479630B2 (en) * | 2017-09-27 | 2022-10-25 | Dic Corporation | Prepreg resin composition, prepreg, and molded article |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4110713A1 (en) * | 1991-04-03 | 1992-10-08 | Basf Ag | TUBULAR COMPONENTS FROM FIBER COMPOSITES |
| DE4126826A1 (en) * | 1991-08-14 | 1993-02-18 | Basf Ag | TOOTH-MODIFIED VINYLESTERURETHANE RESINS |
| FR2737726A1 (en) * | 1995-08-11 | 1997-02-14 | Takeda Chemical Industries Ltd | PREIMPREGNE SHEET AND ARTICLE MOLDED FROM SUCH SHEET |
| FI112877B (en) | 1998-09-10 | 2004-01-30 | Metso Paper Inc | Schaberbett |
| DE102006000139B3 (en) * | 2006-03-28 | 2007-10-18 | Hilti Ag | Hand-guided tacker |
| GB201000182D0 (en) | 2010-01-07 | 2010-02-24 | Hexcel Composites Ltd | Novel curable resins and curing agents therefor |
| BR112013017258A2 (en) * | 2011-01-04 | 2016-10-25 | Evonik Degussa Gmbh | composite semifinished products and molded parts produced therefrom, as well as molded parts produced directly from functionalized hydroxy (meth) acrylates, which are crosslinked by thermofixed urethodiones |
| JP2018052112A (en) * | 2016-09-26 | 2018-04-05 | 日本合成化学工業株式会社 | Multilayer film for fiber bonding and/or fiber sheet surface protection, and thermosetting composition for fiber bonding and/or fiber sheet surface protection |
| JP7047292B2 (en) * | 2016-09-26 | 2022-04-05 | 三菱ケミカル株式会社 | Laminated film for fiber adhesion and / or fiber sheet surface protection |
| JP7359520B2 (en) * | 2018-02-22 | 2023-10-11 | ビーエーエスエフ ソシエタス・ヨーロピア | Polyurethane-based polymer material with excellent thermal deformation resistance and tear elongation |
| TWI794446B (en) * | 2019-03-13 | 2023-03-01 | 日商迪愛生股份有限公司 | Resin composition for prepreg, prepreg and molded article |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4758400A (en) * | 1987-01-27 | 1988-07-19 | Ashland Oil, Inc. | Thermosetting molding compounds |
| DE3744390A1 (en) * | 1987-12-29 | 1989-07-13 | Basf Ag | Fibre composite materials based on modified vinyl ester urethane resins |
-
1990
- 1990-04-24 DE DE4012946A patent/DE4012946A1/en not_active Withdrawn
-
1991
- 1991-03-20 EP EP91104272A patent/EP0458028A1/en not_active Withdrawn
- 1991-03-20 EP EP91104304A patent/EP0454983A1/en not_active Withdrawn
- 1991-04-15 CA CA002039840A patent/CA2039840A1/en not_active Abandoned
- 1991-04-23 JP JP3092092A patent/JPH04227656A/en not_active Withdrawn
- 1991-04-23 JP JP3092091A patent/JPH04227642A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2513207B1 (en) | 2009-12-14 | 2017-05-03 | Gurit (UK) Ltd. | Prepregs for manufacturing composite materials |
| US10538638B2 (en) | 2009-12-14 | 2020-01-21 | Gurit (Uk) Ltd. | Prepregs for manufacturing composite materials |
| US11198281B2 (en) | 2016-09-26 | 2021-12-14 | Mitsubishi Chemical Corporation | Laminated film for fiber adhesion and/or fiber sheet surface protection and thermosetting composition for fiber adhesion and/or fiber sheet surface protection |
| US20200385539A1 (en) * | 2017-09-27 | 2020-12-10 | Dic Corporation | Prepreg resin composition, prepreg and molded article |
| US11479630B2 (en) * | 2017-09-27 | 2022-10-25 | Dic Corporation | Prepreg resin composition, prepreg, and molded article |
| US11760849B2 (en) * | 2017-09-27 | 2023-09-19 | Dic Corporation | Prepreg resin composition, prepreg and molded article |
| CN114539718A (en) * | 2022-02-28 | 2022-05-27 | 山东莱蔚特复合材料有限责任公司 | Preparation method of mould pressing composite material plate spring |
| CN114539718B (en) * | 2022-02-28 | 2024-01-26 | 山东莱蔚特复合材料有限责任公司 | Preparation method of die-pressed composite plate spring |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0458028A1 (en) | 1991-11-27 |
| DE4012946A1 (en) | 1991-10-31 |
| JPH04227642A (en) | 1992-08-17 |
| EP0454983A1 (en) | 1991-11-06 |
| JPH04227656A (en) | 1992-08-17 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued |