CN106749988A - The synthesis technique and purposes of a kind of modified thickening epoxy vinyl ester resin - Google Patents
The synthesis technique and purposes of a kind of modified thickening epoxy vinyl ester resin Download PDFInfo
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- CN106749988A CN106749988A CN201611243706.6A CN201611243706A CN106749988A CN 106749988 A CN106749988 A CN 106749988A CN 201611243706 A CN201611243706 A CN 201611243706A CN 106749988 A CN106749988 A CN 106749988A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The synthesis technique and purposes of modified thickening epoxy vinyl ester resin, the technical problem to be solved is to make low synthesis technique reaction temperature, course of reaction and reaction materil structure easily controllable, final product can be suitably used for SMC/BMC techniques, belong to technical field of high-molecular polymer.Characterized in that, 0.5%~1.5% catalyst dissolution in 6%~15% organic mono unsaturated carboxylic acid；Above-mentioned catalyst organic mono unsaturated carboxylic acid mixed solution is added dropwise in esterification by ring opening reaction；30%~45% cross-linking monomer is first added to dilute before esterification chain extending reaction：1.0%~8.0% acid anhydrides is added, 1~2 hour is incubated, stopped when acid number is up to 30~40 mgKOH/g.The present invention has advantages below：Thickening effect is good, meets SMC/BMC to the quick-setting requirement of resin, when being used from different shrinking agents and function additive collocation, can obtain the characteristics such as high glaze, zero contraction and class-A surfaces.It is hardly damaged or ftractures in SMC/BMC article manufacturing process, can adapt to the die press technology for forming of different condition.
Description
Technical field
The present invention relates to the synthesis technique and purposes of a kind of modified thickening epoxy vinyl ester resin, belong to high molecular polymer
Technical field.
Background technology
SMC/BMC （SMC is sheet molding compound, and BMC is BMC）It is with unsaturated polyester resin, curing agent, increasing
Thick dose, the mould that obtains of the resin paste infiltration chopped mat that mixes such as filler and lower shrinkage/low-contour additive or rove
Binder, can finally realize the characteristics such as the fire-retardant of product, zero contraction and class-A surfaces.The advantage of SMC/BMC techniques is apparent：Produce
Quality stabilization, favorable reproducibility, production efficiency is high, low cost, operating environment cleaning, substantially improves work situation.So making
It is the composite that a kind of efficient mechanical metaplasia is produced, the concern for enjoying composite industrial quarters always till now from being born.
SMC/BMC technological requirement resins have the characteristics that：Modest viscosity, is easy to lay-up；Easy same thickener
Reaction, meets the requirement of thickening；Shrinkage can be reduced；Solidification is rapid, improve production efficiency；With high-temperature capability higher and
Fixed toughness；In article removal, it is hardly damaged or ftractures.
SMC/BMC techniques typically use o-, m- benzene-type unsaturated polyester resin, as product properties requirement is improved, especially
It has been SMC/BMC since commercialization is realized, pursues anti-corrosion, heat-resisting and efficient always, constantly meets modern industry different field
Requirement.But the aspects such as o-, m- benzene-type unsaturated polyester resin product is anti-corrosion, heat resistance and product strength can not meet existing
For the use requirement of industrial development.Although common epoxy vinyl ester resin is substantially better than not in terms of corrosionproof heatproof and intensity
Saturated polyester resin, but it cannot be thickened or thickening effect is undesirable, so as to cause the contraction of product larger, gloss is not very on surface
Occur situations such as thering is crackle to grow dim, it is impossible to for SMC/BMC techniques.
Epoxy vinyl ester resin synthesis reaction temperature is higher, generally greater than 100 DEG C, such as Chinese patent
Mentioned in ZL200610200365.8 fast thickening vinyl ester resins and its production and use, " it is gradually heating to 90 ~
140 DEG C, insulation reaction 2 ~ 6 hours ... adds maleic anhydride, continues to reflect 2 ~ 3 hours ", under such higher temperature,
Reaction is difficult to control to, and easily produces side reaction.
Therefore, be modified thickening epoxy vinyl ester resin synthesis technique, makes low its reaction temperature, course of reaction and reactant
Structure is easily controllable, and final product can be suitably used for SMC/BMC techniques, is not only the effort mesh of the numerous scientific and technical personnel in the field
Mark, and product has the wide market demand and development prospect.
The content of the invention
The purpose of the present invention is：It is the shortcoming or deficiency that overcome prior art to exist, there is provided the modified thickening epoxy second of one kind
The synthesis technique of alkenyl esters resin, makes low its reaction temperature, course of reaction and reaction materil structure easily controllable, and final product is resistant to
Erosion, heat-resisting, thickening effect it is good, suitable for SMC/BMC techniques.
To reach above-mentioned purpose, the technical scheme of use is：A kind of conjunction of modified thickening epoxy epoxy vinyl ester resin
Into technique, it is characterised in that comprise the following steps, in each step, material is by mass percentage：
(1) catalyst dissolution liquid is prepared：0.5%~1.5% catalyst dissolution in 6%~15% organic mono unsaturated carboxylic acid
In, stir, if environment temperature is less than 15 DEG C, heat and control temperature to be not higher than 60 DEG C, it is small that the heat time is no longer than 4
When；
(2) esterification by ring opening reaction：40%~60% epoxy resin and 0.01%~0.05% polymerization inhibitor are put into reactor, nitrogen is protected
The lower stirring of shield, is gradually heating to 70~90 DEG C, and keeping temperature and stirring, and the catalyst organic mono that step (1) is prepared is added dropwise
Unsaturated carboxylic acid mixed solution, drips off for 1~2 hour, 2~3 hours is incubated after dripping, until acid number stops less than 5mgKOH/g；
It is sufficiently stirred for the dilution of the cross-linking monomer of addition 30%~45%；
(3) it is esterified chain extending reaction：40~60 DEG C of keeping temperature, adds 1.0%~8.0% acid anhydrides, is incubated 1~2 hour, and acid number reaches
Stop during 30~40 mgKOH/g；Refilter, be cooled to room temperature, obtain final product Pale yellow viscous liquid SMC/BMC epoxy vinyl esters
Resin.
The epoxy resin refers to one or more in bisphenol A type epoxy resin.
The organic mono unsaturated carboxylic acid is methacrylic acid or acrylic acid.
The catalyst is one or more in imidazoles and/or imidazole salt catalyst.
The polymerization inhibitor is TBHQ, tert-butyl catechol, 1,4-benzoquinone, hydroquinones, methyl to benzene two
One or more in phenol.
The acid anhydrides is maleic anhydride, phthalic anhydride, hydrogen for phthalic anhydride, chlorendic anhydride, equal benzene four
In formic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol double aniline acid anhydrides, methyl cyclohexane alkenyl tetracarboxylic dianhydride and trimellitic anhydrides etc. partially
One or more.
The cross-linking monomer is styrene, divinylbenzene, vinyltoluene, methacrylate, acrylate, adjacent benzene
One or more in diformazan diallyl phthalate.
Described modified thickening epoxy vinyl ester resin is applied to SMC/BMC techniques.
The synthesis technique of the modified thickening epoxy vinyl ester resin of the present invention compared with prior art, with advantages below：
（1）In advance catalyst dissolution in organic mono unsaturated carboxylic acid, and use dripping method so that catalyst and organic one
First unsaturated carboxylic acid can relatively evenly participate in reaction.After avoiding catalyst from disposably putting into, early stage Catalysis Rate quickly, causes anti-
Heat release should be concentrated, is difficult to control, avoid reaction later stage catalyst consumption to finish again, reaction is difficult to carry through to the end.Dissolving in advance, drop
Plus reaction, reaction can be made uniform, heat release is easily controllable, and can reduce the consumption of catalyst and polymerization inhibitor, reduces reaction temperature
Degree, does not extend the reaction time, saves production cost.
（2）The esterification by ring opening reaction of common epoxy resin and organic mono unsaturated carboxylic acid is carried out more than 100 DEG C
, high temperature is also easy to produce side reaction.The present invention is opened using preferred catalyst catalyzed epoxies and organic mono unsaturated carboxylic acid
Ring esterification so that reaction temperature is carried out at 70 ~ 90 DEG C, reduces reaction temperature, does not extend the reaction time, and saving is produced into
This, hence it is evident that reacted better than common esterification by ring opening.
（3）The present invention first dilutes, then carries out the esterification chain extending reaction of acid anhydrides.Can thus avoid producing pair anti-under high temperature
Should, reaction temperature is reduced, do not extend the reaction time, production cost is saved, better control over reactant molecule structure.And can be with
Proper acid number is obtained, for resin thickening.
（4）The epoxy vinyl ester resin resin thickening effect of present invention synthesis is good, can meet SMC/BMC technological requirements.
Common epoxy vinyl ester resin thickening effect is undesirable, and viscosity only can reach 10 within 72 hours4MPas or so.Present invention synthesis
The epoxy vinyl ester resin resin thickening effect substantially, viscosity can reach 10 within 72 hours7More than mPas, with medium or
High reaction activity, meets SMC/BMC to the quick-setting requirement of resin, makes when from different shrinking agents and function additive collocation
Used time, the characteristics such as high glaze, zero contraction and class-A surfaces can be obtained.It is hardly damaged or opens in SMC/BMC article manufacturing process
Split, it is ensured that SMC/BMC products are obtained in that the incomparable high intensity of common unsaturated polyester resin.
Specific embodiment
The present invention is more fully described with reference to embodiment, the optimal implementing process of the present invention is disclosed, it is noted that
The present invention is not limited to the following embodiments for disclosing, and is enlightened based on the present invention, any obvious conversion or equivalent substitute,
Should also be as being considered as to fall into protection scope of the present invention.
Embodiment 1：
Catalyst 2-methylimidazole 9.50g is dissolved in methacrylic acid 135g, is stirred, it is standby.Put into the reactor
Bisphenol A type epoxy resin（Epoxide equivalent is 179 ~ 192g/mol）450g, TBHQ 0.15g.It is passed through the feelings of nitrogen
It is gradually heating to 80 DEG C under condition, keeping temperature and stirring are added dropwise the methacrylic acid solution dissolved with catalyst, drip off within 1 ~ 2 hour,
Acid number is detected after dripping per half an hour, until measuring acid number less than 5mgKOH/g.Add styrene 360g, methyl methacrylate
Ester 20g, methyl hydroquinone 0.05g, is sufficiently stirred for, and adds maleic anhydride 40g, 50 DEG C of keeping temperature and stirring, often
Half an hour detects acid number, until acid number is in 30 ~ 40 mgKOH/g；Room temperature is finally cooled to, filtering obtains final product Pale yellow viscous liquid.
Embodiment 2：
Catalyst 1 benzyl 2 methyl imidazole 11.0g and 2- phenylimidazole 1.5g is dissolved in acrylic acid 86g, is stirred, it is standby
With.Bisphenol A type epoxy resin is put into the reactor（Epoxide equivalent is 185 ~ 196g/mol）430g, 1,4-benzoquinone 0.10g, to benzene
Diphenol 0.10g.It is gradually heating to 90 DEG C in the case of being passed through nitrogen, keeping temperature and stirring are added dropwise the propylene dissolved with catalyst
Acid solution, drips off for 1 ~ 2 hour, detects acid number after dripping per half an hour, until measuring acid number less than 5mgKOH/g.Add benzene second
Alkene 360g, vinyltoluene 70g, is sufficiently stirred for, and adds phthalic anhydride 20g, methyl tetrahydrophthalic anhydride 20g,
45 DEG C of keeping temperature and stirring, acid number are detected per half an hour, until acid number is in 30 ~ 40 mgKOH/g；It is finally cooled to room temperature, mistake
Filter obtains final product Pale yellow viscous liquid.
Embodiment 3：
Catalyst 1,3- dibenzyl -2-methylimidazole chloride 6.8g and dichloride copper 0.5g are dissolved in methacrylic acid 130g
In, stir, it is standby.Bisphenol A type epoxy resin is put into the reactor（Epoxide equivalent is 213 ~ 244g/mol）560g is right
Benzenediol 0.25g.It is gradually heating to 75 DEG C in the case of being passed through nitrogen, keeping temperature and stirring are added dropwise the first dissolved with catalyst
Base acrylic acid solution, drips off for 1 ~ 2 hour, detects acid number after dripping per half an hour, until measuring acid number less than 5mgKOH/g.Plus
Enter styrene 320g, be sufficiently stirred for, add chlorendic anhydride 15g, benzophenone tetracarboxylic dianhydride 20g, 40 DEG C of keeping temperature and stirring, often
Half an hour detects acid number, until acid number is in 30 ~ 40 mgKOH/g；Room temperature is finally cooled to, filtering obtains final product Pale yellow viscous liquid.
Embodiment 4：
Catalyst 1- cyanoethyl -2- undecyl imidazoles 10.0g is dissolved in acrylic acid 75g, is stirred, it is standby.In reaction
Bisphenol A type epoxy resin is put into device（Epoxide equivalent is 250 ~ 330g/mol）520g, tert-butyl catechol 0.15g.It is passed through
It is gradually heating to 90 DEG C in the case of nitrogen, keeping temperature and stirring are added dropwise the acrylic acid solution dissolved with catalyst, 1 ~ 2 hour
Drip off, detect acid number after dripping per half an hour, until measuring acid number less than 5mgKOH/g.Add styrene 400g, adjacent benzene two
Formic acid diallyl 30g, methyl hydroquinone 0.10g, are sufficiently stirred for, and add phthalic anhydride 20g, benzophenone tetracarboxylic dianhydride
15g, 60 DEG C of keeping temperature and stirring, acid number are detected per half an hour, until acid number is in 30 ~ 40 mgKOH/g；It is finally cooled to room
Temperature, filtering obtains final product Pale yellow viscous liquid.
Embodiment 5：
Catalyst 2-methylimidazole 7.5g and copper sulphate 1.0g are dissolved in methacrylic acid 72g, are stirred, it is standby.Anti-
Answer and put into bisphenol A type epoxy resin in device（Epoxide equivalent is 455 ~ 556g/mol）500g, hydroquinones 0.20g.It is passed through nitrogen
In the case of be gradually heating to 80 DEG C, keeping temperature and stirring are added dropwise the methacrylic acid solution dissolved with catalyst, 1 ~ 2 hour
Drip off, detect acid number after dripping per half an hour, until measuring acid number less than 5mgKOH/g.Styrene 400g is added, is fully stirred
Mix, add trimellitic anhydride 15g, pyromellitic dianhydride 15g, 40 DEG C of keeping temperature and stirring, acid number is detected per half an hour,
Until acid number is in 30 ~ 40 mgKOH/g；Room temperature is finally cooled to, filtering obtains final product Pale yellow viscous liquid.
Embodiment 6：
Catalyst 2- undecyl imidazoles 11.5g and dibrominated zinc 0.8g are dissolved in methacrylic acid 60g, are stirred, it is standby
With.Bisphenol A type epoxy resin is put into the reactor（Epoxide equivalent is 550 ~ 1000g/mol）550g, hydroquinones 0.10g,
TBHQ 0.10g.It is gradually heating to 75 DEG C in the case of being passed through nitrogen, keeping temperature and stirring are added dropwise dissolved with urging
The methacrylic acid solution of agent, drips off for 1 ~ 2 hour, detects acid number after dripping per half an hour, is less than until measuring acid number
5mgKOH/g.Styrene 360g, methyl acrylate 50g, methyl hydroquinone 0.05g are added, is sufficiently stirred for, add maleic
Dicarboxylic anhydride 20g, 55 DEG C of keeping temperature and stirring, acid number are detected per half an hour, until acid number is in 30 ~ 40 mgKOH/g；It is last cold
But to room temperature, filtering obtains final product Pale yellow viscous liquid.
The Typical mass index of gained resin is as follows in each embodiment above：
The typical mechanical performance index of the casting resin is as follows：
| Project | Data | Method of testing |
| Tensile strength MPa | 60~80 | GB/T2567 |
| Stretch modulus GPa | 3.0~3.5 | GB/T2567 |
| Elongation at break % | 3~5 | GB/T2567 |
| Bending strength MPa | 110~130 | GB/T2567 |
| Bending modulus GPa | 3.2~3.7 | GB/T2567 |
| Heat distortion temperature DEG C（1.8MPa） | 110~120 | GB/T1634 |
Epoxy vinyl ester resin modest viscosity of the invention, is easy to lay-up；Easily reacted with thickener, meet thickening
Requirement；Shrinkage can be reduced；Solidification is rapid, improve production efficiency；With high-temperature capability and certain toughness higher；In system
During pint mould, it is hardly damaged or ftractures.Epoxy vinyl ester resin of the present invention is entirely capable of meeting the need of all kinds of SMC/BMC products
Ask, adapt to the die press technology for forming of different condition.
Claims (8)
1. it is a kind of it is modified thickening epoxy vinyl ester resin synthesis technique, it is characterised in that：Comprise the following steps, each step
Rapid middle material is by mass percentage：
(1) catalyst dissolution liquid is prepared：0.5%~1.5% catalyst dissolution in 6%~15% organic mono unsaturated carboxylic acid
In, stir, if environment temperature is less than 15 DEG C, heat and control temperature to be not higher than 60 DEG C, it is small that the heat time is no longer than 4
When；
(2) esterification by ring opening reaction：40%~60% epoxy resin and 0.01%~0.05% polymerization inhibitor are put into reactor, nitrogen is protected
The lower stirring of shield, is gradually heating to 70~90 DEG C, and keeping temperature and stirring, and the catalyst organic mono that step (1) is prepared is added dropwise
Unsaturated carboxylic acid mixed solution, drips off for 1~2 hour, 2~3 hours is incubated after dripping, until acid number stops less than 5mgKOH/g；
It is sufficiently stirred for the dilution of the cross-linking monomer of addition 30%~45%；
(3) it is esterified chain extending reaction：40~60 DEG C of keeping temperature, adds 1.0%~8.0% acid anhydrides, is incubated 1~2 hour, and acid number reaches
Stop during 30~40 mgKOH/g；Refilter, be cooled to room temperature, obtain final product Pale yellow viscous liquid epoxy vinyl ester resin.
2. the modified thickening epoxy vinyl ester resin synthesis technique as described in claim 1, it is characterised in that：The asphalt mixtures modified by epoxy resin
Fat refers to one or more in bisphenol A type epoxy resin.
3. the modified thickening epoxy vinyl ester resin synthesis technique as described in claim 1, it is characterised in that：Described organic one
First unsaturated carboxylic acid is methacrylic acid or acrylic acid.
4. the modified thickening epoxy vinyl ester resin synthesis technique as described in claim 1, it is characterised in that：The catalyst
It is one or more in imidazoles and/or imidazole salt catalyst.
5. the modified thickening epoxy vinyl ester resin synthesis technique as described in claim 1, it is characterised in that：The polymerization inhibitor
It is one or more in TBHQ, tert-butyl catechol, 1,4-benzoquinone, hydroquinones, methyl hydroquinone.
6. the modified thickening epoxy vinyl ester resin synthesis technique as described in claim 1, it is characterised in that：The acid anhydrides is
Maleic anhydride, phthalic anhydride, hydrogen are for phthalic anhydride, chlorendic anhydride, pyromellitic dianhydride, benzophenone tetracid two
One or more in acid anhydride, ethylene glycol double aniline acid anhydrides, methyl cyclohexane alkenyl tetracarboxylic dianhydride and trimellitic anhydrides partially.
7. the modified thickening epoxy vinyl ester resin synthesis technique as described in claim 1, it is characterised in that：The crosslinking is single
Body is in styrene, divinylbenzene, vinyltoluene, methacrylate, acrylate, diallyl phthalate
One or more.
8. the modified thickening epoxy vinyl ester resin described in claim 1 is applied to SMC/BMC techniques.
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| CN201611243706.6A CN106749988A (en) | 2016-12-29 | 2016-12-29 | The synthesis technique and purposes of a kind of modified thickening epoxy vinyl ester resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114395089A (en) * | 2022-01-14 | 2022-04-26 | 东莞市比翼新材料科技有限公司 | Compression molding type vinyl resin and preparation method thereof |
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|---|---|---|---|---|
| CN101747491A (en) * | 2009-12-11 | 2010-06-23 | 上海新天和树脂有限公司 | Fast thickening vinyl ester resin as well as preparation method and application thereof |
| CN103304749A (en) * | 2013-07-11 | 2013-09-18 | 华东理工大学华昌聚合物有限公司 | Synthetic method of modified high-toughness epoxy vinyl ester resin |
| CN103497287A (en) * | 2013-09-09 | 2014-01-08 | 华东理工大学华昌聚合物有限公司 | Synthetic technology of epoxy vinyl ester resin for SMC/BMC |
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2016
- 2016-12-29 CN CN201611243706.6A patent/CN106749988A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747491A (en) * | 2009-12-11 | 2010-06-23 | 上海新天和树脂有限公司 | Fast thickening vinyl ester resin as well as preparation method and application thereof |
| CN103304749A (en) * | 2013-07-11 | 2013-09-18 | 华东理工大学华昌聚合物有限公司 | Synthetic method of modified high-toughness epoxy vinyl ester resin |
| CN103497287A (en) * | 2013-09-09 | 2014-01-08 | 华东理工大学华昌聚合物有限公司 | Synthetic technology of epoxy vinyl ester resin for SMC/BMC |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114395089A (en) * | 2022-01-14 | 2022-04-26 | 东莞市比翼新材料科技有限公司 | Compression molding type vinyl resin and preparation method thereof |
| CN114395089B (en) * | 2022-01-14 | 2024-04-16 | 东莞市比翼新材料科技有限公司 | Molded vinyl resin and preparation method thereof |
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