CN101165060A - Method for modifying heat-proof plasticizing methyl nadic anhydride - Google Patents
Method for modifying heat-proof plasticizing methyl nadic anhydride Download PDFInfo
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- CN101165060A CN101165060A CNA200610117185XA CN200610117185A CN101165060A CN 101165060 A CN101165060 A CN 101165060A CN A200610117185X A CNA200610117185X A CN A200610117185XA CN 200610117185 A CN200610117185 A CN 200610117185A CN 101165060 A CN101165060 A CN 101165060A
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Abstract
The process of preparing modified heat resistant toughened methyl nadic anhydride includes heated reaction of methyl nadic anhydride, heat resistant anhydride, toughening agent and catalyst of inorganic acid and/or phosphorus-containing compound in certain weight proportion inside a reactor to obtain liquid coarse product, and flash evaporation of the coarse product in a flash evaporation kettle to obtain heat resistant toughened methyl nadic anhydride product. The process has yield up to 90 %, normal pressure operation and low cost; and modified nadic anhydride has raised heat resistance and toughness.
Description
Technical field:
The present invention relates to chemical field, relate in particular to the acid anhydride type curing agent that is used for epoxy resin cure, particularly methyl carbic anhydride, concrete is a kind of method of modifying of heat-proof plasticizing methyl nadic anhydride.
Background technology:
The methyl carbic anhydride is reacted by methyl cyclopentadiene and cis-butenedioic anhydride and obtains, and its formal name used at school is 4, the different phenylpropyl alcohol furans of 7-endo-methylene group-1,3 diketone-3a α, 4a, 7a, 7a α-tetrahydrochysene methyl, molecular formula: C
10H
10O
3, molecular weight: 178.2, structural formula is as follows:
Because itself and epoxy resin cure after fixing thing are than using methyl tetrahydro phthalic anhydride and epoxy resin cure after fixing thing good heat resistance usually, and the methyl carbic anhydride is the liquid with small viscosity acid anhydrides, long working life with Resins, epoxy mixing back, therefore, obtain widespread use, but for high-performance electronic, electric, insulating material, its resistance toheat also needs further to improve.In addition, epoxy resin cured product is owing to its natural characteristics, and it is not enough that its cured article impact strength also shows, and also needs to overcome cured article fragility, increases cured article toughness.For this reason, add various toughner sometimes, but after adding toughner, tend to influence the cured article resistance toheat.So users' an urgent demand can improve curable epoxide thing resistance toheat, can increase curable epoxide thing toughness again, and product wishes to be to use liquid acid anhydrides easily.
Japanese Patent (JP 0559153) uses the methyl carbic anhydride to handle 3 hours with Sodium Toluene Sulphonate under 180 ℃, reacted 6 hours at 180 ℃ with cis-butenedioic anhydride then, get (I) tetracarboxylic anhydride, add 70 parts of carbic anhydrides with 30 parts (I) and get the modified methyl carbic anhydride, with 100 parts of Resins, epoxy 825,85 parts of modified methyl carbic anhydrides and 2-methyl-4-ethyl imidazol(e) are made promotor curing, 189 ℃ of its cured article fail temperatures, flexural strength 10.4Kg/m
2
Japanese Patent (JP 0559151) uses the methyl carbic anhydride to receive with toluene sulfonic acide under 180 ℃ and handled 3 hours, reacted 6 hours at 180 ℃ with cis-butenedioic anhydride then, get (I) tetracarboxylic anhydride, add 70 parts of Rikacid TH with 30 parts (I) and get the modified methyl carbic anhydride, with 100 parts of Resins, epoxy, 77 parts of modified methyl carbic anhydrides and 2-methyl-4-ethyl imidazol(e) are made promotor curing, 170 ℃ of its cured article fail temperatures, flexural strength 12.2Kg/m
2
Above-mentioned two patented methods improve to methyl carbic anhydride resistance toheat, but flexural strength slightly descends than common methyl carbic anhydride and epoxy resin cured product flexural strength.
Summary of the invention:
The object of the present invention is to provide a kind of method of modifying of heat-proof plasticizing methyl nadic anhydride, the method for modifying of described heat-proof plasticizing methyl nadic anhydride will solve the flexural strength low technical problem of the flexural strength of methyl carbic anhydride in the prior art than common methyl carbic anhydride and epoxy resin cured product.
The method of modifying of this heat-proof plasticizing methyl nadic anhydride of the present invention, comprise that takes by weighing a methyl carbic anhydride in proportion, heat-resisting acid anhydrides, the first step of toughner and catalyzer, second step of carrying out reacting by heating and one carry out flash distillation purified third step, in described first step, described catalyzer is a mineral acid, or P contained compound, or the arbitrary combination of mineral acid and P contained compound, the weight ratio of described methyl carbic anhydride and described heat-resisting acid anhydrides is 1: 0.05～0.40, the weight ratio of described methyl carbic anhydride and described toughner is 1: 0.05～0.35, the weight ratio of described methyl carbic anhydride and described catalyzer is 1: 0.005～5, in described second step, with the methyl carbic anhydride that takes by weighing, heat-resisting acid anhydrides, toughner and catalyzer drop in the reactor and carry out reacting by heating, temperature of reaction is between 50～200 ℃, obtain methyl carbic anhydride liquid crude goods after the reacting by heating, in described third step, described methyl carbic anhydride liquid crude goods are dropped into the flash distillation still, the temperature of described flash distillation still is between 160～250 ℃, and be under the condition of the negative 0.060～0.095Mpa of gauge pressure in vacuum tightness, it is refining to carry out flash distillation, obtains heat-proof plasticizing methyl nadic anhydride.
Further, described catalyzer is a mineral acid, and described mineral acid is selected from sulfuric acid or phosphoric acid or polyphosphoric acid, and the general formula of wherein said polyphosphoric acid is
Wherein n is 1～5.
Further, described catalyzer is constituted by any two kinds of mineral acids in sulfuric acid, phosphoric acid, the polyphosphoric acid, and the weight ratio of described any two kinds of mineral acids is 1: 0.5～1.5.
Further, the weight ratio of described methyl carbic anhydride and described catalyzer is 1: 0.005～1.5.
Further, described catalyzer is a P contained compound, and described P contained compound is selected from phosphorus oxide or phosphine or phosphonic acids, Huo person's phosphonium compounds, and described phosphorus oxide is a Vanadium Pentoxide in FLAKES, and the general formula of described phosphine is:
R1, R2, R3 represent all alkyl of H atom or C1-C5 respectively in the formula, and described phosphonic general formula is:
R1, R2, R3 difference representation hydroxy or alkyl or phenyl in the formula,
Suo Shu De phosphonium compounds general formula is R4PX, and R representation hydrocarbyl in the formula, X representation hydroxy or halogen atom or acid group, described alkyl are all alkyl of C1-C5, and described X is selected from OH-or Cl-or Br-or I-or SO
4=or NO
3-or PO
4≡.
Further, described catalyzer is a P contained compound, and described P contained compound is phosphorus oxide, phosphine, phosphonic acids He the combination of any two kinds of P contained compounds in the phosphonium compounds, and the weight ratio of described any two kinds of P contained compounds is 1: 0.5～1.5.
Further, the weight ratio of described methyl carbic anhydride and described catalyzer is 1: 0.005～2.0.
Further, described catalyzer is the mixture of mineral acid and P contained compound, and the weight ratio of described mineral acid and P contained compound is 1: 0.5～1.5.
Further, the weight ratio of described methyl carbic anhydride and described catalyzer is 1: 0.005～2.0.
Further, described heat-resisting acid anhydrides is selected from pyromellitic acid acid anhydride or trimellitic acid 1,2-anhydride or carbic anhydride or hexachloro endoethylene tetrahydrophthalic acid acid anhydride or benzophenone tetracarboxylic dianhydride or phenyl ether tetracarboxylic dianhydride or tetrahydrotoluene tetracarboxylic dianhydride, or any both combination in the pyromellitic acid acid anhydride, trimellitic acid 1,2-anhydride, carbic anhydride, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, benzophenone tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, tetrahydrotoluene tetracarboxylic dianhydride.
Further, described heat-resisting acid anhydrides is any both combination in pyromellitic acid acid anhydride, trimellitic acid 1,2-anhydride, carbic anhydride, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, benzophenone tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, the tetrahydrotoluene tetracarboxylic dianhydride, and described between the two weight ratio arbitrarily is 1: 0.1～4.0.
Further, described any weight ratio between the two is 1: 0.1～2.
Further, the weight ratio of described methyl carbic anhydride and described heat-resisting acid anhydrides is 1: 0.1～0.3.
Further, described toughner is selected from n-butyl glycidyl ether, perhaps C8-C10 alcohol glycidyl ether, perhaps C12 alcohol glycidyl ether, perhaps C12-C14 alcohol glycidyl ether, perhaps glycol ether glycidyl ether, perhaps hexanediol diglycidyl ether, perhaps polyethyleneglycol diglycidylether, perhaps polypropylene glycol diglycidyl ether, perhaps dihydroxyphenyl propane, perhaps bisphenol S, perhaps strange scholar's toughner, perhaps terminal hydroxy liquid divinyl rubber, perhaps terminal hydroxy liquid butyronitrile rubber, perhaps polyethers, the molecular weight of described polyethers is between 1000-2000.
Further, the weight ratio of described methyl carbic anhydride and described toughner is 1: 0.1～0.25.
Further, the temperature of described flash distillation still is between 160～200 ℃.
Concrete, the methyl carbic anhydride can be with hydroxyl or epoxy reaction in the represented acid anhydride base of general formula and heat-resisting acid anhydrides, the toughner, the methyl carbic anhydride has bridge-type＜endo〉and hanging＜exo two kinds of steric isomers, product is bridge-type and hanging equilibrium mixture, and modified methyl carbic anhydride of the present invention is formed no particular requirement to equilibrium mixture.
The present invention compares with prior art, yield can reach 90%, and reaction does not need pressure, in the presence of catalyzer, only need 50～200 ℃ of reactions down, reaction process is similar to routine with technology, and resultant of reaction is liquid product, and is easy to use, can add more filler, reducing product cost. methyl carbic anhydride thermotolerance and toughness all improve to some extent after the modification, and methyl carbic anhydride and epoxy resin cured product second-order transition temperature are 145～150 ℃ usually, resistance to impact shock 15KJ/M
2The methyl carbic anhydride is because the production cost height, sale price is more expensive, and heat-resisting acid anhydrides, toughner are except that minority, major part is lower than the methyl carbic anhydride, therefore, and after the modification, product thermotolerance and toughness all have suitable raising, but production cost and methyl carbic anhydride maintain an equal level, or slightly descend, and cost performance is outstanding.The methyl carbic anhydride is suitable before its insulating property of methyl carbic anhydride after the modification and the modification.
Embodiment:
Further illustrate substance of the present invention and obvious improvement below by embodiment, but the present invention absolutely not only is confined to embodiment.
Embodiment 1
In Zhuan You Hui flow condenser and feeder and agitator vessel, add methyl carbic anhydride 200g, sulfuric acid 1.0g, phosphenylic acid 1.0g, pyromellitic acid acid anhydride 50g, glycol ether glycidyl ether 40g, under agitation be heated to 160 ℃, reacted 1 hour, then flash distillation under-0.09Mpa vacuum, get the garnet transparent liquid, yield 92%.
Solidity test E51: modified methyl carbic anhydride: 2-ethyl-4-methylimidazole=100: 80.5: 1
100 ℃ of 80 ℃ of deaerations of solidification value half an hour/2h+130 ℃/3h+150 ℃/3h+180 ℃/3h (the solidification value ratio is with reference to " Resins, epoxy and epoxy coating " version in 2003, Chemical Industry Press, P216-P218 page or leaf)
Second-order transition temperature: 175 ℃
Second-order transition temperature it be amorphous or semi-crystalline polymer from viscosity flow or the elastomeric state temperature when glassy transition (or opposite transformation), it represents the size of this polymkeric substance resistance toheat.Adopt thermomechanical analysis to measure the second-order transition temperature of engineering plastics, use thermomechanical analyzer to record the sample inflection curves, make tangent line by temperature-inflection curves again, try to achieve second-order transition temperature (with reference to " engineering plastics handbook (using and the test volume) " in October, 2004 version, China Machine Press, the P955-956 page or leaf).
Resistance to impact shock: 28KJ/m
2(shock strength is represented the maximum capacity that material is hit and loads, under impact load, the ratio that the merit that is consumed during material damage is long-pending with sample cross, shock strength is measured the charpy impact test method/izodtest method etc. that adopts, shock strength is represented the toughness of material quality. (with reference to " engineering plastics handbook (using and the test volume) " in October, 2004 version, China Machine Press, the PL071 page or leaf.)
Embodiment 2
In said apparatus, add methyl carbic anhydride 200g, polyphosphoric acid 1.0g, phosphenylic acid 1.0g, terminal hydroxy group butyronitrile rubber 30g, pyromellitic acid acid anhydride 50g under agitation is heated to 170 ℃, reacts 1.5 hours, flash distillation under-0.09Mpa vacuum then, reddish-brown liquid, yield 92.5%.
Solidity test E51: modified methyl carbic anhydride: 2-ethyl-4-methylimidazole=100: 80: 1
100 ℃ of 80 ℃ of deaerations of solidification value half an hour/2h+130 ℃/3h+150 ℃/3h+180 ℃/3h
Second-order transition temperature: 170 ℃ of resistance to impact shock: 35KJ/m
2
Embodiment 3
In said apparatus, add methyl carbic anhydride 200g, sulfuric acid 1.5g, Qing oxidation Si Jia Phosphonium 0.5g, polypropylene glycol diglycidyl ether 40g, trimellitic acid 1,2-anhydride 50g, under agitation be heated to 165 ℃, reacted 1 hour, then flash distillation under-0.09Mpa vacuum, get the milk yellow opaque liq, yield 92.3%.
Solidity test E51: modified methyl carbic anhydride: 2-ethyl-4-methylimidazole=100: 77: 1
100 ℃ of 80 ℃ of deaerations of solidification value half an hour/2h+130 ℃/3h+150 ℃/3h+180 ℃/3h
Second-order transition temperature: 172 ℃ of resistance to impact shock: 26KJ/m
2
Embodiment 4
In said apparatus, add methyl carbic anhydride 200g, phosphatase 11 .5g, iodate Si Jia Phosphonium 0.5g, terminal hydroxy group divinyl fluid rubber 30g, trimellitic acid 1,2-anhydride 50g, under agitation be heated to 170 ℃, reacted 1.5 hours, then flash distillation under-0.09Mpa vacuum, get newborn pale brown look opaque liq, yield 91%.
Solidity test E51: modified methyl carbic anhydride: 2-ethyl-4-methylimidazole=100: 77: 1
100 ℃ of 80 ℃ of deaerations of solidification value half an hour/2h+130 ℃/3h+150 ℃/3h+180 ℃/3h
Second-order transition temperature: 174 ℃ of resistance to impact shock: 32KJ/m
2
Embodiment 5
In said apparatus, add methyl carbic anhydride 200g, sulfuric acid 1.5g, Qing oxidation Si Jia Phosphonium 0.5g, ethylene glycol diglycidylether 40g, hexachloro endoethylene tetrahydrophthalic acid acid anhydride 50g under agitation is heated to 160 ℃, reacts 1 hour, flash distillation under-0.09Mpa vacuum then, light yellow transparent liquid, yield 92%.
Solidity test E51: modified methyl carbic anhydride: 2-ethyl-4-methylimidazole=100: 90: 1
100 ℃ of 80 ℃ of deaerations of solidification value half an hour/2h+130 ℃/3h+150 ℃/3h+180 ℃/3h
Second-order transition temperature: 166 ℃ of resistance to impact shock: 25KJ/m
2
Embodiment 6
In said apparatus, add methyl carbic anhydride 200g, phosphatase 11 .5g, Vanadium Pentoxide in FLAKES 0.5g, C
12Alcohol diglycidylether 40g, hexachloro endoethylene tetrahydrophthalic acid acid anhydride 50g under agitation is heated to 160 ℃, react 1 hour, and flash distillation under-0.09Mpa vacuum then must light yellow transparent liquid, yield 92.5%.
Solidity test E51: modified methyl carbic anhydride: 2-ethyl-4-methylimidazole=100: 90: 1
100 ℃ of 80 ℃ of deaerations of solidification value half an hour/2h+130 ℃/3h+150 ℃/3h+180 ℃/3h
Second-order transition temperature: 171 ℃ of resistance to impact shock: 30KJ/m
2
Reference examples 1
Solidity test E51: methyl carbic anhydride: 2-ethyl-4-methylimidazole=100: 82.5: 1
100 ℃ of 80 ℃ of deaerations of solidification value half an hour/2h+130 ℃/3h+150 ℃/3h+180 ℃/3h
Second-order transition temperature: 148 ℃ of resistance to impact shock: 15KJ/m
2Flexural strength: 13.5Kg/mm
2
Reference examples 2
Solidity test E51: methyl tetrahydro phthalic anhydride: 2-ethyl-4-methylimidazole=100: 85: 1
100 ℃ of 80 ℃ of deaerations of solidification value half an hour/2h+130 ℃/3h+150 ℃/2h
Second-order transition temperature: 125 ℃ of resistance to impact shock: 12KJ/m
2Flexural strength: 13.0Kg/mm
2
Claims (16)
1. the method for modifying of a heat-proof plasticizing methyl nadic anhydride, it is characterized in that: described method of modifying comprises that takes by weighing a methyl carbic anhydride in proportion, heat-resisting acid anhydrides, the first step of toughner and catalyzer, second step of carrying out reacting by heating and one carry out flash distillation purified third step, in described first step, described catalyzer is a mineral acid, or P contained compound, or the arbitrary combination of mineral acid and P contained compound, the weight ratio of described methyl carbic anhydride and described heat-resisting acid anhydrides is 1: 0.05～0.40, the weight ratio of described methyl carbic anhydride and described toughner is 1: 0.05～0.35, the weight ratio of described methyl carbic anhydride and described catalyzer is 1: 0.005～5, in described second step, with the methyl carbic anhydride that takes by weighing, heat-resisting acid anhydrides, toughner and catalyzer drop in the reactor and carry out reacting by heating, temperature of reaction is between 50～200 ℃, obtain methyl carbic anhydride liquid crude goods after the reacting by heating, in described third step, described methyl carbic anhydride liquid crude goods are dropped into the flash distillation still, the temperature of described flash distillation still is between 160～250 ℃, and be under the condition of the negative 0.060～0.095Mpa of gauge pressure in vacuum tightness, it is refining to carry out flash distillation, obtains heat-proof plasticizing methyl nadic anhydride.
2. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 1, it is characterized in that: described catalyzer is a mineral acid, and described mineral acid is selected from sulfuric acid or phosphoric acid or polyphosphoric acid, and the general formula of wherein said polyphosphoric acid is
Wherein n is 1～5.
3. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 2, it is characterized in that: described catalyzer is constituted by any two kinds of mineral acids in sulfuric acid, phosphoric acid, the polyphosphoric acid, and the weight ratio of described any two kinds of mineral acids is 1: 0.5～1.5.
4. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 3, it is characterized in that: the weight ratio of described methyl carbic anhydride and described catalyzer is 1: 0.005～1.5.
5. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 1, it is characterized in that: described catalyzer is a P contained compound, described P contained compound is selected from phosphorus oxide or phosphine or phosphonic acids, Huo person's phosphonium compounds, described phosphorus oxide is a Vanadium Pentoxide in FLAKES, and the general formula of described phosphine is:
R in the formula
1, R
2, R
3Represent all alkyl of H atom or C1-C5 respectively,
Described phosphonic general formula is:
R in the formula
1, R
2, R
3Difference representation hydroxy or alkyl or phenyl,,
Suo Shu De phosphonium compounds general formula is R
4PX, R representation hydrocarbyl in the formula, X representation hydroxy or halogen atom or acid group, described alkyl are all alkyl of C1-C5, described X is selected from OH
-, or Cl
-, or Br
-, or I
-, or SO4
=, or NO3
-, or PO4
≡
6. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 5, it is characterized in that: described catalyzer is a P contained compound, described P contained compound is phosphorus oxide, phosphine, phosphonic acids He the combination of any two kinds of P contained compounds in the phosphonium compounds, and the weight ratio of described any two kinds of P contained compounds is 1: 0.5～1.5.
7. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 6, it is characterized in that: the weight ratio of described methyl carbic anhydride and described catalyzer is 1: 0.005～2.0.
8. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 1, it is characterized in that: described catalyzer is the mixture of mineral acid and P contained compound, the weight ratio of described mineral acid and P contained compound is 1: 0.5～1.5.
9. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 8, it is characterized in that: the weight ratio of described methyl carbic anhydride and described catalyzer is 1: 0.005～2.0.
10. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 1, it is characterized in that: described heat-resisting acid anhydrides is selected from pyromellitic acid acid anhydride or trimellitic acid 1,2-anhydride or carbic anhydride or hexachloro endoethylene tetrahydrophthalic acid acid anhydride or benzophenone tetracarboxylic dianhydride or phenyl ether tetracarboxylic dianhydride or tetrahydrotoluene tetracarboxylic dianhydride, or any both combination in the pyromellitic acid acid anhydride, trimellitic acid 1,2-anhydride, carbic anhydride, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, benzophenone tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, tetrahydrotoluene tetracarboxylic dianhydride.
11. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 10, it is characterized in that: described heat-resisting acid anhydrides is any both combination in pyromellitic acid acid anhydride, trimellitic acid 1,2-anhydride, carbic anhydride, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, benzophenone tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, the tetrahydrotoluene tetracarboxylic dianhydride, and described between the two weight ratio arbitrarily is 1: 0.1～4.0.
12. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 11 is characterized in that: described any weight ratio between the two is 1: 0.1～2.
13. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 10 is characterized in that: the weight ratio of described methyl carbic anhydride and described heat-resisting acid anhydrides is 1: 0.1～0.3.
14. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 1 is characterized in that: described toughner is selected from n-butyl glycidyl ether or C
8-C
10Alcohol glycidyl ether or C
12Alcohol glycidyl ether or C
12-C
14Alcohol glycidyl ether or glycol ether glycidyl ether or hexanediol diglycidyl ether or polyethyleneglycol diglycidylether or polypropylene glycol diglycidyl ether or dihydroxyphenyl propane or bisphenol S or strange scholar's toughner or terminal hydroxy liquid divinyl rubber or terminal hydroxy liquid butyronitrile rubber or polyethers, the molecular weight of described polyethers is between 1000-2000.
15. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 14 is characterized in that: the weight ratio of described methyl carbic anhydride and described toughner is 1: 0.1～0.25.
16. the method for modifying of heat-proof plasticizing methyl nadic anhydride as claimed in claim 1 is characterized in that: the temperature of described flash distillation still is between 160～200 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206325A (en) * | 2010-03-31 | 2011-10-05 | 朱瑞澄 | Modification method of heat-resistant toughened methyl tetrahydrophthalic anhydride |
| CN105906814A (en) * | 2016-06-13 | 2016-08-31 | 四川大学 | Epoxy-terminated polyether and preparation method thereof and application thereof to serve as epoxy resin toughening agent |
-
2006
- 2006-10-16 CN CNA200610117185XA patent/CN101165060A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206325A (en) * | 2010-03-31 | 2011-10-05 | 朱瑞澄 | Modification method of heat-resistant toughened methyl tetrahydrophthalic anhydride |
| CN102206325B (en) * | 2010-03-31 | 2012-09-05 | 朱瑞澄 | Modification method of heat-resistant toughened methyl tetrahydrophthalic anhydride |
| CN105906814A (en) * | 2016-06-13 | 2016-08-31 | 四川大学 | Epoxy-terminated polyether and preparation method thereof and application thereof to serve as epoxy resin toughening agent |
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