CN1195669A - Rigidity plastics based on isocyanate and preparing method thereof - Google Patents
Rigidity plastics based on isocyanate and preparing method thereof Download PDFInfo
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- CN1195669A CN1195669A CN97106367A CN97106367A CN1195669A CN 1195669 A CN1195669 A CN 1195669A CN 97106367 A CN97106367 A CN 97106367A CN 97106367 A CN97106367 A CN 97106367A CN 1195669 A CN1195669 A CN 1195669A
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- acid
- unsaturated polyester
- polyester resin
- isocyanic ester
- alcohol
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- 239000004033 plastic Substances 0.000 title claims abstract description 19
- 229920003023 plastic Polymers 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000012948 isocyanate Substances 0.000 title abstract description 4
- 150000002513 isocyanates Chemical class 0.000 title abstract description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 230000032050 esterification Effects 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 150000007520 diprotic acids Chemical class 0.000 claims description 10
- 238000011417 postcuring Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- -1 Ethenyl Chemical class 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 5
- 238000013461 design Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 2
- 235000011037 adipic acid Nutrition 0.000 claims 1
- 239000001361 adipic acid Substances 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- 238000012644 addition polymerization Methods 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention discloses a kind of rigid plastics using isocyanate as base material. It is characterized by that said invention uses dibasic alcohol and binary acid according to the alcohol-acid mole ratio of 1.5/1-2.0/1 to make them produce reaction to obtain hydroxyl-capped unsaturated polyester resin; then utilizes the addition polymerization of crosslinking agent whose weight is 20-50% of weight of the unsaturated polyester and said unsaturated polyester resin and the condensation polymerization between the hydroxyl on the unsaturated polyester resin and isocyanate whose index is 90-120 to produce a three dimensional net structure. Said invention is simple in technological process, short in hardening time, and possesses excellent mechanical property, thermal property and electric property.
Description
The present invention relates to the high molecular synthetic technology 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, and this material is leading in electrical equipment embedding insulation field with its excellent thermal characteristics and electrical property, so people still use it as main embedding insulating material at present.But the Resins, epoxy production cycle is long, and 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 has occupied critical positions in people's life, but the requirement that its anti-electric heating resistance can 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 make it respectively with unsaturated polyester, Resins, epoxy, vinyl ester resin is made interpenetrating(polymer)networks, 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 diprotic acid 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:
With the isocyanic ester is the preparation method of the rigidity plastics of base, and it is characterized in that: a. esterification is synthesized 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
1And diprotic acid, under 180 ℃～220 ℃, carry out esterification, when the acid number of reaction mixture is reduced to 5mgKOH/g when following, system is evacuated to 0～2mmHg, make esterification proceed and extract out micromolecular water and unreacted small molecular alcohol, by measuring the acid number of resultant, reduce to 0.5mgKOH/g when following when acid number, be considered as reaction and finish.Measure the hydroxyl value of unsaturated polyester resin and calculate molecular weight; B. complex reaction generates single network.Its processing condition are as follows: unsaturated polyester resin is dewatered, and processing condition are: 80～95 ℃ of temperature, pressure 0～2mmHg, time: 2～4 hours; 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 the technology of post curing as follows: open mould after in 80～90 ℃ of baking ovens, solidifying 6～10 minutes, 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.It is simple that the present invention has technology, the characteristics that set time is short, and, can add mineral fillers such as filling silica powder when needing to reduce cost because the viscosity of mixture is low, opened up the Application Areas of polyurethane material, quickened the development of embedding insulating material technology as the embedding insulating material.
Below the 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 by: by dibasic alcohol R
1React with 1.5/1～2.0/1 molar ratio of alcohol to acid with diprotic acid 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:
Wherein: 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 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, DAP resin for vinylbenzene, other benzene.
With the isocyanic ester is the preparation method of the rigidity plastics of base, utilizes esterification synthesis of hydroxy end-blocking unsaturated polyester earlier, its chemical reaction skeleton symbol:
R wherein
1Be dibasic alcohol; R
3Be monounsaturated dicarboxylic acid.The feed ratio of dibasic alcohol and diprotic acid is determined according to the size of 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
1And diprotic acid, under 180 ℃～220 ℃, carry out esterification, diprotic acid is made up of with 1/1 mol ratio unsaturated dibasic acid (or acid anhydrides) and monounsaturated dicarboxylic acid (or acid anhydrides), when the acid number of reaction mixture is reduced to 5mgKOH/g when following, system is evacuated to 0～2mmHg, make esterification proceed and extract out micromolecular water and unreacted small molecular alcohol, by measuring the acid number of resultant, reduce to 0.5mgKOH/g when following when acid number, be considered as reaction when promptly level of response to 99.8% is above and finish.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:
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). the dehydration of unsaturated polyester resin.Processing condition are as follows:
Temperature: 80～95 ℃; Pressure: 0～2mmHg, the time: 2～4 hours.
(2). add the linking agent dilution.Reduce temperature of charge, linking agent is added in the unsaturated polyester according to a certain percentage, stirs 15～20 minutes mixings.
(3). temperature of charge is cooled to below 20 ℃, add unsaturated polyester and linking agent overall weight percent and be 0.5～2% initiator and index and be 90～120 isocyanic ester, be evacuated to 0～2mmHg 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, and material is cast in the mould of 80～90 ℃ of preheatings.
(4). condition of cure and post curing technology.
Condition of cure: solidify after 6～10 minutes in 80～90 ℃ of baking ovens and open mould.
Post curing technology: sample sent in 100 ℃ the baking oven post curing 1～2 hour.
For further proof technological process of the present invention, exemplifying the performance of following embodiment and product: embodiment 1. is the system of the unsaturated polyester and the rigidity plastics thereof of dibasic alcohol with the glycol ether
Be equipped with:
Step 1. is carried out the synthetic unsaturated polyester resin 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 glycol ethers (452.13g)
1.42 moles of Tetra hydro Phthalic anhydrides (210.16g)
1.42 moles of MALEIC ANHYDRIDE (139.16g)
At first system is cleaned with drying nitrogen, add glycol ether and phthalic anhydride again, 180 ℃ of reactions down, by measuring the acid number of 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 2mmHg, progressively be warming up to 200 ℃, reacted 3 hours and extract micromolecular water out and unreacted small molecular alcohol, reduce to 0.5mgKOH/g when following, be considered as reaction and finish when acid number.
(4). measure the hydroxyl value of unsaturated polyester and calculate molecular weight.
Step 2: generate single network by complex reaction with polyphenyl polymethylene polyisocyanates (PAPI) and HUPR.The chemical reaction skeleton symbol:
(1) the ammonia esterification generates the urethane long-chain:
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:
R wherein
1For
--CH
2CH
2---O---CH
2CH
2---R
2For
(annotate: MEKP is a methylethyl ketone peroxide) its processing condition are as follows:
(1). the dehydration of unsaturated polyester.Processing condition are as follows:
Temperature: 80～95 ℃; Pressure: 0～2mmHg; Time: 2～4 hours.
(2). add the vinylbenzene dilution.Temperature of charge is controlled at 80 ℃, and vinylbenzene is added in the unsaturated polyester according to a certain percentage, stirs 20 minutes mixings.
(3). add initiator and isocyanic ester.Temperature of charge is cooled under 20 ℃, adds the 1%wt of unsaturated polyester and vinylbenzene gross weight.Initiator and index be 105 isocyanic ester PAPI, be evacuated to 2mmHg and stirred 1 minute fast, stop to stir and continuing to vacuumize 2～3 minutes, stop to vacuumize after the no bubble appearance to the material, and material be cast in the mould of 80 ℃ of preheatings.
(4). condition of cure and post curing technology.
Condition of cure: solidify after 10 minutes in 80 ℃ of baking ovens and open mould.
Post curing technology: sample sent in 100 ℃ the baking oven post curing 2 hours.Embodiment 2. is with the 2-methyl isophthalic acid, and ammediol is the system of the unsaturated polyester and the rigidity plastics thereof of dibasic alcohol
Be equipped with: the prescription and the technology of synthesis of hydroxy end-blocking unsaturated polyester (HUPR2):
The 2-methyl isophthalic acid, 3 moles of ammediols (270g)
1 mole of Tetra hydro Phthalic anhydride (148g)
1 mole of MALEIC ANHYDRIDE (98g)
Single network of the synthetic rigidity plastics of unsaturated polyester synthesis technique and complex reaction is all 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
Annotate: a) basic recipe is in parts by weight;
| Embodiment | ????1 | ????2 |
| Basic recipe a | ||
| ????HUPR | ????100(HUPR1 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 | ????81.4 | ????81.48 |
| Flexural strength/N/mm 2 | ????218.0 | ????155 |
| Shock strength/KJ/m 2 | ????24.33 | ????13.02 |
| Tensile yield/% | ????11.3 | ????9.53 |
| Electrical property | ||
| Specific inductivity (1MHz) | ????3.4 | ????3.4 |
| Dielectric loss (1MHz) | ????0.017 | ????0.029 |
| Volume resistance/Ω cm | ????3.1 *10 14 | ????1.0 *10 14 |
| 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 |
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-, ammediol synthetic unsaturated polyester resin;
D) PAPI refers to polyphenyl polymethylene polyisocyanates;
E) MEKP is meant methylethyl ketone peroxide-dimethyl phthalate solution of 60%.
Claims (6)
1. be 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 diprotic acid 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 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, DAP resin for vinylbenzene, other benzene.
3. be the preparation method of the rigidity plastics of base with the isocyanic ester, it is characterized in that:
A. esterification is synthesized 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
1And diprotic acid, under 180 ℃～220 ℃, carry out esterification, when the acid number of reaction mixture is reduced to 5mgKOH/g when following, system is evacuated to 0～2mmHg, make esterification proceed and extract out micromolecular water and unreacted small molecular alcohol, by measuring the acid number of resultant, reduce to 0.5mgKOH/g when following when acid number, be considered as reaction and finish.Measure the hydroxyl value of unsaturated polyester resin and calculate molecular weight.
B. complex reaction generates single network.Its processing condition are as follows: unsaturated polyester resin is dewatered, and processing condition are: 80～95 ℃ of temperature, pressure 0～2mmHg, time: 2～4 hours; 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 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 of 80～90 ℃ of preheatings.
C. be cured and the technology of post curing as follows: open mould after in 80～90 ℃ of baking ovens, solidifying 6～10 minutes, 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, ammediol, 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, adipic acid; Linking agent R
4Ethenyl derivatives, DAP resin for vinylbenzene, other benzene.
By claim 3 or 4 described be the preparation method of rigidity plastics of base with the isocyanic ester, it is characterized in that: diprotic acid is made up of with 1/1 mol ratio unsaturated dibasic acid (or acid anhydrides) and monounsaturated dicarboxylic acid (or acid anhydrides).
6. 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106367A CN1073580C (en) | 1997-04-08 | 1997-04-08 | Rigidity plastics based on isocyanate and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106367A CN1073580C (en) | 1997-04-08 | 1997-04-08 | Rigidity plastics based on isocyanate and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN1195669A true CN1195669A (en) | 1998-10-14 |
| CN1073580C CN1073580C (en) | 2001-10-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106367A Expired - Fee Related CN1073580C (en) | 1997-04-08 | 1997-04-08 | Rigidity plastics based on isocyanate and preparing method thereof |
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| Country | Link |
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| CN (1) | CN1073580C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100569829C (en) * | 2002-12-24 | 2009-12-16 | 德古萨公司 | Dispersion based on unsaturated polyester resin some tristane dimethanol isomer, that amorphous and ammonia are ester modified |
| CN101151293B (en) * | 2005-03-30 | 2010-12-08 | 三井化学聚氨酯株式会社 | Two-component curable water-based urethane alkyd resin composition and its application |
| 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 |
| CN103665311A (en) * | 2013-08-22 | 2014-03-26 | 常州大学 | Modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method |
| CN104448792A (en) * | 2014-12-29 | 2015-03-25 | 青岛瑞诺化工有限公司 | Electronic component encapsulating material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1182423A (en) * | 1966-06-16 | 1970-02-25 | Tercol Ltd | Improvements relating to Polymer Compositions |
| DE2848401A1 (en) * | 1978-11-08 | 1980-06-12 | Hoechst Ag | CURABLE DIMENSIONS AND METHOD FOR THEIR PRODUCTION |
| JPS60146235A (en) * | 1984-01-11 | 1985-08-01 | Toray Ind Inc | Photosensitive resin for printing plate |
| JP2547087B2 (en) * | 1989-01-18 | 1996-10-23 | 荒川化学工業株式会社 | Method for producing polyurethane acrylate |
| JPH0674306B2 (en) * | 1990-04-13 | 1994-09-21 | 昭和高分子株式会社 | Low shrinkage resin composition |
-
1997
- 1997-04-08 CN CN97106367A patent/CN1073580C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100569829C (en) * | 2002-12-24 | 2009-12-16 | 德古萨公司 | Dispersion based on unsaturated polyester resin some tristane dimethanol isomer, that amorphous and ammonia are ester modified |
| CN101151293B (en) * | 2005-03-30 | 2010-12-08 | 三井化学聚氨酯株式会社 | Two-component curable water-based urethane alkyd resin composition and its application |
| 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 |
| CN103665311A (en) * | 2013-08-22 | 2014-03-26 | 常州大学 | Modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method |
| 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 |
| CN104448792A (en) * | 2014-12-29 | 2015-03-25 | 青岛瑞诺化工有限公司 | Electronic component encapsulating material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1073580C (en) | 2001-10-24 |
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