CN1073580C - Rigidity plastics based on isocyanate and preparing method thereof - Google Patents

Rigidity plastics based on isocyanate and preparing method thereof Download PDF

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CN1073580C
CN1073580C CN97106367A CN97106367A CN1073580C CN 1073580 C CN1073580 C CN 1073580C CN 97106367 A CN97106367 A CN 97106367A CN 97106367 A CN97106367 A CN 97106367A CN 1073580 C CN1073580 C CN 1073580C
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acid
unsaturated polyester
polyester resin
isocyanic ester
linking agent
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CN1195669A (en
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王得宁
杲云
肖桂普
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The present invention discloses rigid plastic using isocyanate as a base. The present invention is characterized in that dihydric alcohol R1 and binary acid react according to an alkyd molar ratio of 1.5/1 to 2.0/1 to obtain hydroxy terminated unsaturated polyester resin, a cross-linking agent R4 whose weight is 20 to 50% of that of polyester and the unsaturated polyester resin carry out addition polymerization, and hydroxyl of the unsaturated polyester resin and isocyanate R2 with an index of 90 to 120 carry out polycondensation to generate an idiotype network structure. The present invention has the advantages of simple manufacturing process, short curing time, excellent mechanical properties, excellent thermal properties and excellent electrical properties and develops the application area that polyurethane material is used as the encapsulating insulating material.

Description

It with the isocyanic ester rigidity plastics of base and preparation method thereof
The present invention relates to the high molecular synthetic technology of chemical industry aspect, specifically a kind of is the rigidity plastics and preparation method thereof of base with the isocyanic ester.
Traditional electrical equipment embedding insulating material is a Resins, epoxy, this material is leading in electrical equipment embedding insulating material field with its excellent thermal characteristics and electrical property, but the Resins, epoxy production cycle is long, the toughness of material difference also is that production industry needs problem demanding prompt solution always, urethane is since being exploited, because its with short production cycle and special physical and chemical performance, in living, people occupied important position, but the requirement that its anti-electricity, resistance toheat do not reach electrical equipment potting material.For many years, people utilize various means doing a large amount of work aspect the modification of Resins, epoxy and urethane, for example utilize the ductile structure of urethane to make it make interpenetrating(polymer)networks with unsaturated polyester, vinyl ester resin respectively, the somebody utilizes isocyanic ester and Resins, epoxy reaction to make high heat-resisting De oxazolidone, the performance of polyurethane material is had increased significantly, but these method complex process cost an arm and a leg, be difficult to realize industrialization, be unfavorable for widespread use.
The object of the present invention is to provide a kind of is the rigidity plastics of base with the isocyanic ester, and it can overcome deficiency of the prior art.
Technical scheme of the present invention is achieved in that with the isocyanic ester to be that basic rigidity plastics is characterized in that: by dibasic alcohol R 1React with 1.5/1～2.0/1 molar ratio of alcohol to acid with the mixture of forming with 1: 1 mol ratio by unsaturated dibasic acid (or acid anhydrides) and monounsaturated dicarboxylic acid (or acid anhydrides) and to obtain hydroxy-end capped unsaturated polyester resin, again with the linking agent R that accounts for this weight polyester per-cent 20～50% 4With the polyaddition reaction of unsaturated polyester resin and the hydroxyl on the unsaturated polyester resin and index be 90～120 isocyanic ester R 2Between polycondensation generate an idiotype network structure, its chemical structure is:
Figure C9710636700051
With the isocyanic ester is the preparation method of the rigidity plastics of base, it is characterized in that: a. esterification is synthesized the terminal hydroxy group unsaturated polyester resin, method is as follows: earlier system is cleaned with drying nitrogen, added the dibasic alcohol R of 1.5/1～2.0/1 molar ratio of alcohol to acid again according to the size of the molecular weight of the unsaturated polyester resin of design 1Reach the mixture of forming with 1/1 mol ratio by unsaturated dibasic acid (or acid anhydrides) and monounsaturated dicarboxylic acid (or acid anhydrides), under 180～220 ℃, carry out esterification, when the acid number of reaction mixture is reduced to 5mgKOH/g, system is evacuated to 0～2mmHg, make esterification proceed and extract out micromolecular water and unreacted small molecular alcohol, when acid number is brought down below 0.5mgKOH/g, is considered as reaction and finishes.Measure the hydroxyl value of unsaturated polyester resin and calculate molecular weight; B. complex reaction generates single network, and its processing condition are as follows: unsaturated polyester resin is dewatered, and processing condition are: 80～95 ℃ of temperature, pressure 0～2mmHg, 2～4 hours time; Add linking agent R again 4Dilution reduces temperature of charge, and linking agent is pressed 20～50% of unsaturated polyester resin weight percent and added and stirring and evenly mixing; Temperature of charge is cooled under 20 ℃, and the initiator of 0.5～2% weight percent of adding unsaturated polyester and linking agent total amount and index are 90～120 isocyanic ester R 2, be evacuated to 0～2mmHg and quick the stirring about 1 minute, stop stirring and continue to be evacuated in the material stopping to vacuumize after the no bubble appearance, material is cast in the mould that is preheated to 80～90 ℃; Be cured and post curing technology as follows: in 80～90 ℃ baking oven, solidify after 6～10 minutes and open mould, send in 100 ℃ the baking oven post curing 1～2 hour again.
The present invention elder generation synthetic molecular weight is 100～2000 hydroxy-end capped unsaturated polyester resin HUPR, dilute through linking agent, with isocyanate reaction, in same reaction system, utilize polycondensation that forms carbamate and the polyaddition reaction that forms the unsaturated polyester network simultaneously, single stage method synthesizes the rigidity plastics with single network structure, and this unique chemical structure is given mechanical property, thermal characteristics and the electrical property of this novel material excellence.Technology of the present invention is simple, and set time is short, and because the viscosity of mixture is low, can fill mineral filler such as silica powder when needing to reduce cost, and has opened up the Application Areas of urethane as the embedding insulating material, quickens the development of embedding insulating material technology.
Below the present invention will be further described and provide embodiment.
The present invention be a kind of with the isocyanic ester be the base rigidity plastics, it is characterized in that: by diprotic acid R 1React with 1.5/1～2.0/1 molar ratio of alcohol to acid with the mixture of forming with 1: 1 mol ratio by unsaturated dibasic acid (or acid anhydrides) and monounsaturated dicarboxylic acid (or acid anhydrides) and to obtain hydroxy-end capped unsaturated polyester resin, again with the linking agent R that accounts for this weight polyester per-cent 20～50% 4With the polyaddition reaction of unsaturated polyester resin and the hydroxyl on the unsaturated polyester resin and index be 90～120 isocyanic ester R 2Between polycondensation generate an idiotype network structure, its chemical structure is:
Figure C9710636700061
Wherein: R 1Be glycol ether, 2-methyl isophthalic acid, ammediol, 1,4-butyleneglycol, ethylene glycol, 1,2-propylene glycol, the perhaps mixture of above-mentioned dibasic alcohol; Isocyanic ester R 2Be tolylene diisocyanate TDI, MDI MDI, polyphenyl polymethylene polyisocyanates PAPI, naphthalene diisocyanate NDI, hexamethylene diisocyanate HDI or modification MDI; Monounsaturated dicarboxylic acid R 3Be phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid; Linking agent R 4Ethenyl derivatives, Phthalic acid, diallyl ester DAP for vinylbenzene, other benzene.
The preparation method who with the isocyanic ester is the rigidity plastics of base is to utilize the end capped unsaturated polyester of esterification synthesis of hydroxy earlier, its chemical reaction skeleton symbol:
Figure C9710636700071
R wherein 1Be dibasic alcohol, R 3Be monounsaturated dicarboxylic acid.The feed ratio of dibasic alcohol and diprotic acid determines that according to the molecular weight of the unsaturated polyester resin of design the molecular weight of unsaturated polyester resin is generally 100～2000.Earlier system is cleaned with drying nitrogen, added the dibasic alcohol R of 1.5/1～2.0/1 molar ratio of alcohol to acid again according to the size of the molecular weight of the unsaturated polyester resin of design 1Reach the mixture of forming with 1/1 mol ratio by unsaturated dibasic acid (or acid anhydrides) and monounsaturated dicarboxylic acid (or acid anhydrides), under 180～220 ℃, carry out esterification, when the acid number of reaction mixture is reduced to 5mgKOH/g, system is evacuated to 0～2mmHg, make esterification proceed and extract out micromolecular water and unreacted small molecular alcohol, when acid number is brought down below 0.5mgKOH/g, is considered as reaction when promptly level of response to 99.8% is above and finishes.Measure the hydroxyl value of unsaturated polyester resin and calculate molecular weight; Complex reaction generates single network again, and the reaction skeleton symbol is as follows:
(1) the ammonia esterification generates the urethane long-chain:
Figure C9710636700072
Because R 2Functionality may be greater than 2, can occur a certain amount of crosslinked in the molecular structure.(2) radical polymerization generates macroreticular:
The concrete operations step is as follows:
(1) dehydration of unsaturated polyester resin.Processing condition are as follows:
80～95 ℃ of temperature, pressure 0～2mmHg, 2～4 hours time.
(2) add the linking agent dilution, reduce temperature of charge, linking agent adds by 20～50% of unsaturated polyester resin weight percent and stirs 15～20 minutes mixings.
(3) temperature of charge is cooled to below 20 ℃, add 0.5～2% initiator of unsaturated polyester and linking agent gross weight and index and be 90～120 isocyanic ester, be evacuated to 0～2mmHg and quick the stirring 1 minute, stop to stir and continue to vacuumize and stopped to vacuumize after the no bubble appearance to the material in 2～3 minutes, and material is cast in the mould that is preheated to 80～90 ℃.
(4) condition of cure and post curing technology.
Condition of cure: solidify in 80～90 ℃ the baking oven after 6～10 minutes and open mould.
Post curing technology: sample sent in 100 ℃ the baking oven post curing 1～2 hour.
In order further to prove technological process of the present invention, exemplify the performance of following embodiment and product.
Embodiment 1, is the preparation of the unsaturated polyester and the rigidity plastics thereof of dibasic alcohol with the glycol ether.
Step 1 is carried out the synthetic unsaturated polyester resin (HUPR1) of esterification,
(1) used diprotic acid (acid anhydride) is made up of with 1/1 mol ratio Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE;
(2) glycol ether and acid anhydrides feed intake with 1.5/1 mol ratio; Material proportion: 4.26 moles of 1.42 moles of 1.42 moles of (210.16g) MALEIC ANHYDRIDE of (452.13g) Tetra hydro Phthalic anhydride of glycol ether (139.16g)
At first system is cleaned with drying nitrogen, add glycol ether and phthalic anhydride again, 180 ℃ of reactions down, by the acid number of assaying reaction resultant, when level of response to 60%, the temperature to 100 of reduction system ℃ adds cis-butenedioic anhydride, 180 ℃ of reactions 1.5 hours down, 200 ℃ were reacted 2 hours down, 210 ℃ were reacted 2 hours down, and 220 ℃ were reacted 1 hour down, stop heating when acid number is reduced to 5mgKOH/g;
(3) vacuumize further reduction acid number, be evacuated to 0～2mmHg, progressively be warming up to 200 ℃, reacted 3 hours and extract micromolecular water out and unreacted small molecular alcohol, when acid number is brought down below 0.5mgKOH/g, be considered as reaction and finish;
(4) measure the hydroxyl value of unsaturated polyester resin and calculate molecular weight.
Step 2 generates single network with polyphenyl polymethylene polyisocyanates (PAPI) and HUPR1 by complex reaction,
The reaction skeleton symbol is as follows:
(1) the ammonia esterification generates the urethane long-chain:
Figure C9710636700091
Because R 2(PAPI) functionality can occur a certain amount of crosslinked greater than 2 in the molecular structure.(2) radical polymerization generates macroreticular: linking agent adopts vinylbenzene here, and the chemical reaction skeleton symbol is as follows:
Figure C9710636700101
R wherein 1For-CH 2CH 2-O-CH 2CH 2-R 2For
Figure C9710636700102
(annotate: MEKP is the dimethyl phthalate solution of methylethyl ketone peroxide)
Its processing condition are as follows:
(1) dehydration of unsaturated polyester resin:
80～90 ℃ of temperature, pressure 0～2mmHg, 2～4 hours time;
(2) add the vinylbenzene dilution, temperature of charge is controlled at 80 ℃, and vinylbenzene is added in the unsaturated polyester resin by a certain percentage, stirs 20 minutes mixings;
(3) add initiator and isocyanic ester, temperature of charge is cooled to below 20 ℃, add 1% initiator of unsaturated polyester and vinylbenzene gross weight and index and be 105 isocyanic ester PAPI, be evacuated to 2mmHg and quick the stirring 1 minute, stop to stir and continuing to vacuumize 2～3 minutes, no bubble stops to vacuumize after occurring to the material, material is cast in the mould that is preheated to 80 ℃;
(4) condition of cure and post curing technology:
Condition of cure: solidify after 10 minutes in 80 ℃ the baking oven and open mould.
Post curing technology: sample sent in 100 ℃ the baking oven post curing 2 hours.
Embodiment 2, and with the 2-methyl isophthalic acid, 3 propylene glycol are the preparation of the unsaturated polyester and the rigidity plastics thereof of dibasic alcohol.
The prescription and the technology of synthesis of hydroxy end-blocking unsaturated polyester resin (HUPR2):
The 2-methyl isophthalic acid, 3 moles of ammediols (270g)
1 mole of Tetra hydro Phthalic anhydride (148g)
The technology of the synthetic rigidity plastics list network of 1 mole of (98g) unsaturated polyester synthesis technique of MALEIC ANHYDRIDE and complex reaction is identical with embodiment 1.
Shown in the prescription of embodiment 1,2 and performance see the following form.
The prescription of embodiment 1,2, performance table look-up
Embodiment 1 2
Basic recipe a：
HUPR 100(HU.PR1 b) 100(HUPR2 c)
PAPI d 30.3 21.5
Vinylbenzene 40 45
MEKP e 1.4 1.4
Mechanical property:
Modulus (MPa) 1131.7 903.4
Tensile strength (MPa) 88.4 81.48
Flexural strength (N/mm 2) 218.0 155.0
Shock strength KJ/M 2) 24.33 13.02
Tensile yield (%) 11.3 9.53
Electrical property
Specific inductivity (MHz) 3.4 3.4
Dielectric loss (MHz) 0.017 0.029
Volume resistance (Ω cm) 3.1*1014 1.0*1014
Surface resistivity (Ω) 2.2*10 14 2.4*10 14
Voltage breakdown (KV/mm) 17.6 17.7
Thermal characteristics
Heat decomposition temperature/℃ 422.2 413.9
Second-order transition temperature/℃ 58.1 60
Annotate: a) basic recipe is in parts by weight;
B) HUPR1 refers to the glycol ether to be dibasic alcohol synthetic unsaturated polyester resin;
C) HUPR2 refers to the methyl isophthalic acid with 2-, and ammediol is a dibasic alcohol synthetic unsaturated polyester resin;
D) PAPI refers to polyphenyl polymethylene polyisocyanates
E) MEKP is the dimethyl phthalate solution of methylethyl ketone peroxide

Claims (5)

1, is the rigidity plastics of base with the isocyanic ester, it is characterized in that: by dibasic alcohol R 1React with 1.5/1～2.0/1 molar ratio of alcohol to acid with the mixture of forming with 1: 1 mol ratio by unsaturated dibasic acid (or acid anhydrides) and monounsaturated dicarboxylic acid (or acid anhydrides) and to obtain hydroxy-end capped unsaturated polyester resin, again with the linking agent R that accounts for this weight polyester per-cent 20～50% 4With the polyaddition reaction of unsaturated polyester resin and the hydroxyl on the unsaturated polyester resin and index be 90～120 isocyanic ester R 2Between polycondensation generate an idiotype network structure, its chemical structure is:
2, described by claim 1 is the rigidity plastics of base with the isocyanic ester, it is characterized in that dibasic alcohol R 1Be glycol ether, 2-methyl isophthalic acid, ammediol, 1,4-butyleneglycol, ethylene glycol, 1,2-propylene glycol, the perhaps mixture of above-mentioned dibasic alcohol; Isocyanic ester R 2Be tolylene diisocyanate TDI, MDI MDI, polyphenyl polymethylene polyisocyanates PAPI, naphthalene diisocyanate NDI, hexamethylene diisocyanate HDI or modification MDI; Monounsaturated dicarboxylic acid R 3Be phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid; Linking agent R 4Ethenyl derivatives, Phthalic acid, diallyl ester DAP for vinylbenzene, other benzene
3, be the preparation method of the rigidity plastics of base with the isocyanic ester, it is characterized in that:
The synthetic terminal hydroxy group unsaturated polyester resin of a, esterification: earlier system is cleaned with drying nitrogen, added the dibasic alcohol R of 1.5/1～2.0/1 molar ratio of alcohol to acid again according to the size of the molecular weight of the unsaturated polyester resin of design 1And the mixture of forming with 1/1 mol ratio by unsaturated dibasic acid (or acid anhydrides) and monounsaturated dicarboxylic acid (or acid anhydrides), under 180～220 ℃, carry out esterification, when the acid number of reaction mixture is reduced to 5mgKOH/g, system is evacuated to 0～2mmHg, make esterification proceed and extract out micromolecular water and unreacted small molecular alcohol, when acid number was brought down below 0.5mgKOH/g, visual response finished, and measured the hydroxyl value of unsaturated polyester resin and calculated molecular weight;
B, complex reaction generate single network: its processing condition are as follows: with unsaturated polyester resin dewater, 80～95 ℃ of temperature, pressure 0～2mmHg, 2～4 hours time; Add linking agent R 4Dilution reduces temperature of charge, and linking agent is pressed 20～50% of unsaturated polyester resin weight percent and added and stirring and evenly mixing; Temperature of charge is cooled to below 20 ℃, and the initiator of 0.5～2% weight percent of adding unsaturated polyester and linking agent total amount and index are 90～120 isocyanic ester R 2, be evacuated to 0～2mmHg and quick the stirring about 1 minute, stop stirring and continue to be evacuated in the material stopping to vacuumize after the no bubble appearance, material is cast in the mould that is preheated to 80～90 ℃;
C, be cured and the technology of post curing as follows: in 80～90 ℃ baking oven, solidify after 6-10 minute and open mould, send in 100 ℃ the baking oven post curing 1-2 hour again.
4, described by claim 3 is the preparation method of the rigidity plastics of base with the isocyanic ester, it is characterized in that: dibasic alcohol R 1Be glycol ether, 2-methyl isophthalic acid, 3 propylene glycol, 1,4-butyleneglycol, ethylene glycol, 1,2-propylene glycol, the perhaps mixture of above-mentioned dibasic alcohol; Isocyanic ester R 2Be TDI, MDI, PAPI, NDI, HDI or modification MDI; Monounsaturated dicarboxylic acid R 3Be phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid; Linking agent R 4Ethenyl derivatives, Phthalic acid, diallyl ester DAP for vinylbenzene, other benzene
5, described by claim 3 is the preparation method of the rigidity plastics of base with the isocyanic ester, and it is characterized in that: initiator adopts peroxide initiator or azo initiator.
CN97106367A 1997-04-08 1997-04-08 Rigidity plastics based on isocyanate and preparing method thereof Expired - Fee Related CN1073580C (en)

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Publication number Priority date Publication date Assignee Title
DE10261005A1 (en) * 2002-12-24 2004-07-08 Degussa Ag Dispersions of amorphous, urethanized unsaturated polyester resins based on certain dicidol isomers
WO2006109432A1 (en) * 2005-03-30 2006-10-19 Mitsui Chemicals Polyurethanes, Inc. Two-component curable aqueous urethane-alkyd resin composition and use thereof
CN103396525A (en) * 2013-07-22 2013-11-20 南通天和树脂有限公司 Unsaturated polyester resin for high-impact-resistance car bumper
CN103665311B (en) * 2013-08-22 2016-04-13 常州大学 A kind of dibasic alcohol preparation method of modified polyurethane/unsaturated polyester resin
CN104448792B (en) * 2014-12-29 2019-08-23 青岛瑞诺化工有限公司 A kind of electronic component package material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1182423A (en) * 1966-06-16 1970-02-25 Tercol Ltd Improvements relating to Polymer Compositions
EP0011216A1 (en) * 1978-11-08 1980-05-28 Hans-Joachim Dr. Kiessling Hardenable masses, process for the production of shaped articles therefrom and their utilization
JPS60146235A (en) * 1984-01-11 1985-08-01 Toray Ind Inc Photosensitive resin for printing plate
JPH02189323A (en) * 1989-01-18 1990-07-25 Arakawa Chem Ind Co Ltd Photocurable resin composition
JPH03294323A (en) * 1990-04-13 1991-12-25 Showa Highpolymer Co Ltd Resin composition having low shrinkage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1182423A (en) * 1966-06-16 1970-02-25 Tercol Ltd Improvements relating to Polymer Compositions
EP0011216A1 (en) * 1978-11-08 1980-05-28 Hans-Joachim Dr. Kiessling Hardenable masses, process for the production of shaped articles therefrom and their utilization
JPS60146235A (en) * 1984-01-11 1985-08-01 Toray Ind Inc Photosensitive resin for printing plate
JPH02189323A (en) * 1989-01-18 1990-07-25 Arakawa Chem Ind Co Ltd Photocurable resin composition
JPH03294323A (en) * 1990-04-13 1991-12-25 Showa Highpolymer Co Ltd Resin composition having low shrinkage

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