CN1657566A - Fibre reinforced vinyl ester resin base pultrusion composite - Google Patents
Fibre reinforced vinyl ester resin base pultrusion composite Download PDFInfo
- Publication number
- CN1657566A CN1657566A CN 200410039473 CN200410039473A CN1657566A CN 1657566 A CN1657566 A CN 1657566A CN 200410039473 CN200410039473 CN 200410039473 CN 200410039473 A CN200410039473 A CN 200410039473A CN 1657566 A CN1657566 A CN 1657566A
- Authority
- CN
- China
- Prior art keywords
- vinyl ester
- composite materials
- resin
- pultrusion
- pultrusion composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Moulding By Coating Moulds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
A fibre reinforced vinylester-resin composition with high toughness, strength and high-temp resistance is prepared from the refractory vinylester-resin composition prepared from phenolic vinylester resin, biphenol-A vinylester resin, solidifying agent and additive, and the reinforcing fibres chosen from carbon fibres, glass fibres, aramide fibres and their mixture through pulling and extruding.
Description
Technical field
The present invention relates to a kind of resistant to elevated temperatures fiber-reinforced resin matrix compound material, especially for the fiber reinforcement Vinyl Ester Resin Composites of pultrusion.
Background technology
Pultrusion composite materials is composited by various resins and high-performance fiber pultrusion, space flight and aviation, Infrastructure and industrial circle have been widely used in, as carbon fiber and resin coiled rod through the pultrusion preparation, have high-strength, lightweight, antifatigue, corrosion resistant characteristics, become the novel material of the Oil extraction that solves high-water-cut oil-producing well, deep-well, ultra deep well and corrosion well.But along with the every increase of the degree of depth of oil well 100m, the temperature on stratum will improve 3 ℃, when setting depth of pump during at 3500m, the temperature of the mixture of crude oil and water has just reached 120 ℃ in the oil well, this special occasions needs long-term resistant to elevated temperatures pultrusion composite materials, therefore, the reisn base material of matrix material should have high strength, corrosion resistant basic characteristics, also resistance and high temperature resistance property must be arranged.The heat resistance of resin matrix has determined the heat resistance of matrix material, vinyl ester resin has characteristics such as excellent mechanical property, thermotolerance, erosion resistance and fast setting because of it at present, and become the main resin matrix of pultrusion composite materials, but thermotolerance is difficult to satisfy the requirement of higher use temperature, at 136 ℃, its matrix material can only be in the medium-term and long-term use of the environment below 90 ℃ as general bisphenol A-type vinyl ester resin second-order transition temperature.Though can improve the thermotolerance of polymer matrix composites by following several approach: comprise the amine modification, boric acid modified, aromatic modified, the molybdenum modification, polyimide modified, phosphorus modification, benzoxazine compound modification and cyanic acid esterification modification, but pultrude process is comparatively harsh to performance requriementss such as the viscosity of resin, curing speed, wetting properties, stable, successive pultrude process requirement that many method of modifying can not satisfy.A kind of heat-stable vinyl ester resin constituent is disclosed as Japanese Patent JP1266120, adopt novolac epoxy-methacrylic ester, Resins, epoxy-methacrylic ester, vinylbenzene, Vinylstyrene reaction back to cooperate and form heat-stable vinyl ester resin constituent with additive, improved the thermotolerance of vinyl ester resin, but this method complex manufacturing, be mainly used in die press technology for forming, be difficult on the pultrusion production technique, directly adopt.U.S. Pat 4480077 discloses a kind of heat-resisting vinyl ester resin, improve thermotolerance by adding unsaturated vinyl monomer and dicyclopentadiene in vinyl ester resin, but the toughness that can cause matrix material reduces, impact strength decreased, the pultrusion composite materials of preparation can not satisfy high performance sucker rod and use.
Summary of the invention
For further improving the resin-based thermotolerance of conventional pultrusion composite materials, and the mechanics and the pultrude process performance of maintenance matrix material, the invention provides a kind of high-temperature fibre of pultrusion molding process that is applicable to and strengthen Vinyl Ester Resin Composites, the resin base system of this matrix material not only has good resistance toheat, and viscosity is low, good with the wetting property of fiber, can directly apply to pultrusion molding process, the matrix material of pultrusion preparation has kept good snappiness, higher interlaminar shear strength.
Main technical schemes: the present invention is to be matrix with the vinyl ester resin compositions, and continuous fibre is for strengthening body, and with the matrix material of pultrusion method preparation, wherein: the resin combination main ingredient is:
Count by weight:
50～95 parts of phenol aldehyde type vinyl ester resins
5～50 parts of bisphenol A-type vinyl ester resins
0.8～2 part in solidifying agent
Contain releasing agent in addition, additive is an amount of.
Wherein solidifying agent is made up of one or more organic peroxy compounds, and additive comprises mineral filler, reactive thinner and the radical polymerization inhibitor that 300 orders are above, can be wherein one or more.
Fiber reinforced material comprises one or more combinations of successive carbon fiber, glass fibre, aramid fiber.Prepare fibre-reinforced Vinyl Ester Resin Composites by the pultrusion die of heating behind the fiber impregnated resin.
Effect of the present invention:
1, the present invention adopts phenol aldehyde type vinyl ester resin and the reaction of bisphenol A-type vinyl ester resin co-curing, and its cured article had both embodied the resistant to elevated temperatures characteristics of phenol aldehyde type vinyl ester resin, had the good fiber wetness of bisphenol A-type vinyl ester resin again; The cross-linking density of homogeneous broadens the cross-linking density distribution range when having changed single resin solidification behind the different resin co-curing of two kinds of structures, has played the effect that absorbs striking energy, has improved the fragility that the fire resistant resin based composites is had.And the phenolic aldehyde segment provides good resistance toheat in the cross-linked network, makes matrix material have good resistance to elevated temperatures and mechanical property simultaneously.
2. the present invention also possesses the processing characteristics of pultrusion in the mechanical property that keeps high heat resistance and excellence.The solidification process of vinyl ester resin is free radical effect homopolymerization and the copolyreaction down that produces by solidifying agent, and its curing reaction characteristic can change by the heat release of mensuration curing system and realizes.When the proportioning and consumption one timing of resin and solidifying agent, the technology stability in the time of can predicting resin pultrusion production according to intensification DSC curve exothermic peak position, exothermic peak temperature scope is that the pultrusion process is formulated processing parameter.The pultrude process of polymer matrix composites requires resin solidification speed moderate, and too fast and slow excessively curing reaction all is unfavorable for the realization of pultrusion process, and the curing reaction speed of resin shows as the size of exothermic peak temperature scope on DSC.Fig. 1 is the different curing exotherm characteristic of resin system under same heat-up rate, as can be seen, the exothermic peak of fire resistant resin composition is between two virgin resin exothermic peaks, and only show a peak, and form regular variation with blend, the thermodynamic compatibility that the fire resistant resin composition is described is good, is the Raolical polymerizable of thermal initiation, can be directly used in pultrude process.
Fig. 2-Fig. 4 is Electronic Speculum (SEM) photo of the pultrusion composite materials crimped section of three kinds of different matrix.The crimped section of fire resistant resin composition/carbon-fibre composite is neat as can be seen, and being significantly improved of the more single resin composite materials of interface performance of resin and fiber is described.
Description of drawings:
Fig. 1 is the different curing exotherm rational curve of resin system under same heat-up rate, and wherein curve 1 is the curve (NVE) of phenol aldehyde type vinyl ester resin; Curve 2 is a bisphenol A-type vinyl ester resin curve (VE); Curve 3,4 is respectively 50.50,75.25 o'clock exothermic character curve for VE/NVE weight ratio of the present invention.
The electromicroscopic photograph of Fig. 2 bisphenol A-type vinyl ester resin/carbon fiber pultrusion composite materials crimped section
Fig. 3 is the electromicroscopic photograph of fire resistant resin composition/carbon fiber pultrusion composite materials crimped section
Fig. 4 is the electromicroscopic photograph of phenol aldehyde type vinyl ester resin/carbon fiber pultrusion composite materials crimped section
Embodiment
Pultrusion composite materials of the present invention comprises continuous fortifying fibre and vinyl ester resin compositions, the main ingredient of therein ethylene base ester resin composition is counted by weight and is contained: 50～95 parts of phenol aldehyde type vinyl ester resins, 5～50 parts of bisphenol A-type vinyl ester resins, 0.8～2 part in organo-peroxide solidifying agent, contain releasing agent 1-3 part in addition, additive 0-5 part, wherein the organo-peroxide solidifying agent is selected for use according to required curing speed and resin composition, can form by one or more organic peroxy compounds, as: peroxy dicarbonate two (4-tertiary butyl cyclohexyl ester), peroxidized t-butyl perbenzoate, releasing agent is general resin forming releasing agent, as: INT-PS125 (trade(brand)name, the U.S. produces), additive comprises the mineral filler that 300 orders are above, reactive thinner and radical polymerization inhibitor, can be wherein one or more, can play the effect of technology stability when regulating composite material pultrusion.
Above-mentioned vinyl ester resin compositions by weight after the proportioning mixing and stirring, is injected the steeping vat of extruding equipment.Fiber reinforced material is one or more combinations of successive carbon fiber, glass fibre, aramid fiber, and the consumption of continuous fibre is similar with general pultrusion composite materials, and its volumn concentration accounts for the ratio of pultrusion composite materials between 55%-65%.Pultrusion die by heating behind the fiber impregnated resin causes vinyl ester resin generation curing reaction under 80～160 ℃ of temperature, prepare fibre-reinforced Vinyl Ester Resin Composites.
Embodiment 1
High temperature resistant vinyl ester resin compositions composed as follows:
50 parts of phenol aldehyde type vinyl ester resins (Fuchem-890)
50 parts of bisphenol A-type vinyl ester resins (Ashland H-922)
2 parts in organo-peroxide solidifying agent
Wherein: peroxy dicarbonate two (4-tertiary butyl cyclohexyl ester)
(trade(brand)name Perkadox-16): 0.5 part
Peroxidized t-butyl perbenzoate (trade(brand)name Trigonox-C): 1.5 parts
3 parts of releasing agents (trade(brand)name INT-PS125)
After above component mixing and stirring, inject the steeping vat of extruding equipment.Fiber reinforced material is the T300-12K carbon fiber, makes the carbon fiber enhancement resin base unidirectional composite material, and the cross section is wide to be 6mm, and thick is 2mm, and wherein the volume content of carbon fiber is 65%.The pultrude process process stabilization, the interlaminar shear strength 76MPa of goods, 153 ℃ of second-order transition temperatures (Tg) can be at life-time service below 120 ℃.
Embodiment 2
High temperature resistant vinyl ester resin compositions composed as follows:
75 parts of phenol aldehyde type vinyl ester resins
25 parts of bisphenol A-type vinyl ester resins
1.2 parts in organo-peroxide solidifying agent
Peroxy dicarbonate two (4-tertiary butyl cyclohexyl esters) wherein
(trade(brand)name Perkadox-16): 0.3 part
Peroxidized t-butyl perbenzoate (trade(brand)name Trigonox-C): 0.9 part
1 part of releasing agent INT-PS125
1 part of nanometer SiO2 filler
After above component mixing and stirring, inject the steeping vat of extruding equipment.Fiber reinforced material is the T300-12K carbon fiber and is coated on the outer field glasscloth of carbon fiber, and goods are the banded coiled rod of the flat of cross section 32mm * 4.2mm, and the volume content of fiber is 60%.The pultrude process process stabilization, the interlaminar shear strength 78MPa of goods, 155 ℃ of second-order transition temperatures (Tg).
Embodiment 3
High temperature resistant vinyl ester resin compositions composed as follows:
95 parts of phenol aldehyde type vinyl ester resins
5 parts of bisphenol A-type vinyl ester resins
0.8 part in organo-peroxide solidifying agent
Perkadox-16:0.2 part wherein
Trigonox-C:0.6 part
2 parts of releasing agent INT-PS125
1 part of 300 order pearl filler
2 parts of 300 order filling aluminium hydrates
2 parts of reactive thinner MMA
0.005 part of hydroquinone of polymerization retarder
After above component mixing and stirring, inject the steeping vat of extruding equipment.Fiber reinforced material is a T300-12K carbon fiber and be coated on the outer field aryl fiber cloth of carbon fiber, and goods are the flat bar of cross section 32mm * 4.2mm, and the volume content of fiber is 55%.The pultrude process process stabilization, the interlaminar shear strength 79MPa of goods, 162 ℃ of second-order transition temperatures (Tg) can be at life-time service below 120 ℃.
Embodiment 4
High temperature resistant vinyl ester resin compositions composed as follows:
Phenol aldehyde type vinyl ester resin (the Fuchem-898 trade mark resin of Shanghai Fu Chen company) proportioning sees Table 1
Bisphenol A-type vinyl ester resin HETRON922, U.S. Ya Shilan company proportioning sees Table 1
0.8 part in organo-peroxide solidifying agent
Perkadox-16:0.2 part wherein
Trigonox-C:0.6 part
2 parts of releasing agent INT-PS125
1 part of 300 order pearl filler
2 parts of 300 order filling aluminium hydrates
2 parts of reactive thinner MMA
0.005 part of hydroquinone of polymerization retarder
After above component mixing and stirring, inject the steeping vat of extruding equipment.Fiber reinforced material is a T300-12K carbon fiber and be coated on the outer field aryl fiber cloth of carbon fiber, and goods are the flat bar of cross section 32mm * 4.2mm, and the volume content of fiber is 55%.The carbon fiber of the different proportionings that make, the performance of polymer matrix composites see Table 1.
The mechanics of the vinyl ester resin compositions/carbon-fibre composite of the different proportionings of table 1 and thermal characteristics
| Resin ratio (Fuchem-898 HETRON-922) | Interlaminar shear strength (MPa) | Flexural strength (MPa) | Modulus in flexure (GPa) | ????Tg ????(℃) |
| Pure 898 | ????72 | ????1972 | ????143 | ????175 |
| ????8∶2 | ????81 | ????1962 | ????142 | ????165 |
| ????6∶4 | ????75 | ????1950 | ????139 | ????158 |
| ????5∶5 | ????73 | ????1883 | ????138 | ????152.5 |
| Pure 922 | ????74 | ????1752 | ????133 | ????136 |
Claims (8)
1, a kind of fiber reinforcement vinyl ester resin base pultrusion composite materials, with the vinyl ester resin compositions is matrix, continuous fibre is for strengthening body, and with the matrix material of pultrusion method preparation, it is characterized in that: the resin combination main ingredient is counted by weight and contained:
50～95 parts of phenol aldehyde type vinyl ester resins
5～50 parts of bisphenol A-type vinyl ester resins
0.8～2 part in solidifying agent
Contain releasing agent in addition, additive is an amount of.
2, matrix material according to claim 1 is characterized in that: count by weight in the resin combination and contain: 1～3 part of releasing agent, 0～5 part of additive.
3, matrix material according to claim 1 is characterized in that: continuous fibre is a kind of or its assorted fibre of carbon fiber, glass fibre, aramid fiber.
4, pultrusion composite materials according to claim 1 is characterized in that: the consumption of continuous fibre is by its volumn concentration, and the ratio that accounts for its pultrusion composite materials is between 55%-65%.
5 pultrusion composite materials according to claim 1 is characterized in that: solidifying agent is one or more compositions of organic peroxy compound.
6, according to claim 1,5 described pultrusion composite materials, it is characterized in that: solidifying agent is two (4-tertiary butyl cyclohexyl ester) and/or peroxidized t-butyl perbenzoates of peroxy dicarbonate.
7, pultrusion composite materials according to claim 1 is characterized in that: additive comprises the mineral filler that one or more 300 orders are above.
8, according to claim 1,7 described pultrusion composite materials, it is characterized in that: additive is aluminium hydroxide, lime carbonate, nano silicon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100394739A CN100351070C (en) | 2004-02-16 | 2004-02-16 | Fibre reinforced vinyl ester resin base pultrusion composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100394739A CN100351070C (en) | 2004-02-16 | 2004-02-16 | Fibre reinforced vinyl ester resin base pultrusion composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1657566A true CN1657566A (en) | 2005-08-24 |
| CN100351070C CN100351070C (en) | 2007-11-28 |
Family
ID=35007279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100394739A Expired - Fee Related CN100351070C (en) | 2004-02-16 | 2004-02-16 | Fibre reinforced vinyl ester resin base pultrusion composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100351070C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831141A (en) * | 2010-04-13 | 2010-09-15 | 山东省阳信丰源科技有限公司 | Double-curing resin matrix for pultrusion process and composite material |
| CN103273668A (en) * | 2013-06-07 | 2013-09-04 | 南通和泰通讯器材有限公司 | Aramid fiber indoor optical fiber cable strengthening core preparation method |
| CN103849119A (en) * | 2012-12-06 | 2014-06-11 | 禹州市远大塑料电器有限责任公司 | High-heat-resistance and low-expansion-coefficient carbon fiber vinyl ester composite material and preparation method thereof |
| CN107286590A (en) * | 2017-08-01 | 2017-10-24 | 合肥利裕泰玻璃制品有限公司 | A kind of corrosion-resistant fiberglass composite |
| CN107631002A (en) * | 2017-08-11 | 2018-01-26 | 常熟市明瑞针纺织有限公司 | A kind of wear-resistant vibration-damping compiles flower cam |
| CN108120670A (en) * | 2016-11-29 | 2018-06-05 | 上海大学 | The test of fiber resin composite material interface shearing performance and ameliorative way under high temperature |
| CN109504331A (en) * | 2018-10-30 | 2019-03-22 | 武汉市科达云石护理材料有限公司 | A kind of two-part room temperature curing adhesive and preparation method thereof |
| CN112063120A (en) * | 2020-08-03 | 2020-12-11 | 中国建筑股份有限公司 | Vinyl resin light composite material and preparation method thereof |
| CN115109375A (en) * | 2022-07-25 | 2022-09-27 | 北京理工大学 | Glass fiber reinforced flame-retardant vinyl ester resin composite material and preparation method thereof |
| CN116218150A (en) * | 2023-03-31 | 2023-06-06 | 武汉联影医疗科技有限公司 | Matching material and application and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07165850A (en) * | 1993-12-16 | 1995-06-27 | Showa Shell Sekiyu Kk | Resin composition for frp pultrusion |
| JPH07179536A (en) * | 1993-12-21 | 1995-07-18 | Showa Shell Sekiyu Kk | Resin composition for frp pultrusion |
| JPH07179542A (en) * | 1993-12-21 | 1995-07-18 | Showa Shell Sekiyu Kk | Resin composition for frp pultrusion |
| CN1171003C (en) * | 1999-08-20 | 2004-10-13 | 山东工业大学 | Flexible continuous band type carbon fiber sucker rod and connector thereof |
| CN1350023A (en) * | 2001-11-05 | 2002-05-22 | 张传国 | Thermosetting composite carbon fiber material and its prepn and use |
| CN1367303A (en) * | 2002-03-05 | 2002-09-04 | 胜利油田长龙橡塑有限责任公司 | Continuous glass fibre reinforced plastic pumping band for oil production and connector |
-
2004
- 2004-02-16 CN CNB2004100394739A patent/CN100351070C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831141A (en) * | 2010-04-13 | 2010-09-15 | 山东省阳信丰源科技有限公司 | Double-curing resin matrix for pultrusion process and composite material |
| CN103849119A (en) * | 2012-12-06 | 2014-06-11 | 禹州市远大塑料电器有限责任公司 | High-heat-resistance and low-expansion-coefficient carbon fiber vinyl ester composite material and preparation method thereof |
| CN103849119B (en) * | 2012-12-06 | 2016-08-24 | 禹州市远大塑料电器有限责任公司 | High heat resisting low expansion coefficient carbon fiber vinyl ester composites and preparation method |
| CN103273668A (en) * | 2013-06-07 | 2013-09-04 | 南通和泰通讯器材有限公司 | Aramid fiber indoor optical fiber cable strengthening core preparation method |
| CN103273668B (en) * | 2013-06-07 | 2015-08-19 | 南通和泰通讯器材有限公司 | The preparation method of aramid fiber inside cable strengthening core |
| CN108120670A (en) * | 2016-11-29 | 2018-06-05 | 上海大学 | The test of fiber resin composite material interface shearing performance and ameliorative way under high temperature |
| CN107286590A (en) * | 2017-08-01 | 2017-10-24 | 合肥利裕泰玻璃制品有限公司 | A kind of corrosion-resistant fiberglass composite |
| CN107631002A (en) * | 2017-08-11 | 2018-01-26 | 常熟市明瑞针纺织有限公司 | A kind of wear-resistant vibration-damping compiles flower cam |
| CN109504331A (en) * | 2018-10-30 | 2019-03-22 | 武汉市科达云石护理材料有限公司 | A kind of two-part room temperature curing adhesive and preparation method thereof |
| CN112063120A (en) * | 2020-08-03 | 2020-12-11 | 中国建筑股份有限公司 | Vinyl resin light composite material and preparation method thereof |
| CN112063120B (en) * | 2020-08-03 | 2022-06-17 | 中国建筑股份有限公司 | Vinyl resin light composite material and preparation method thereof |
| CN115109375A (en) * | 2022-07-25 | 2022-09-27 | 北京理工大学 | Glass fiber reinforced flame-retardant vinyl ester resin composite material and preparation method thereof |
| CN116218150A (en) * | 2023-03-31 | 2023-06-06 | 武汉联影医疗科技有限公司 | Matching material and application and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100351070C (en) | 2007-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9920161B2 (en) | Epoxy systems for composites | |
| JP5403184B1 (en) | Fiber reinforced composite material | |
| CN103965582B (en) | For carbon nano double cured resin matrix and the matrix material of pultrusion molding process | |
| CN111655766B (en) | Fiber-reinforced molded article and method for producing same | |
| TWI491683B (en) | Graphene composite coating layer | |
| CN102220029A (en) | High heat-resistant fiber reinforcement vinyl ester composite material with low expansion coefficient | |
| CN100351070C (en) | Fibre reinforced vinyl ester resin base pultrusion composite | |
| TW201734081A (en) | Latent epoxy resin formulations for liquid impregnation processes for production of fibre composite materials | |
| CN101831141A (en) | Double-curing resin matrix for pultrusion process and composite material | |
| CN102964780A (en) | Epoxy resin composition for vacuum introduction formation of fibre reinforced composite material and preparation method of epoxy resin composition | |
| CN1324257C (en) | Bamboo-plastic composite pipe shaping method | |
| Artemenko et al. | Polymer composite materials based on carbon, basalt, and glass fibres | |
| CA1303273C (en) | Optimum formulation regions of reinforced thermoset composites | |
| CN1213084C (en) | Preparation method and application of modified double maleimide resin | |
| CN109161194A (en) | A kind of fishing rod high-strength tenacity composite material | |
| CN1762686A (en) | Self-reinforced interlayer shearing intensity resin base fiber reinforced composite material preparation method | |
| JP2015163468A (en) | Method for producing molded article and molded article | |
| CN1239608C (en) | Special epoxy resin material for compressed natural gas cylinder | |
| JP2005126723A (en) | Composite material and method for manufacturing the same | |
| CN103160088A (en) | Carbon fiber reinforced unsaturated polyester molding compound | |
| CN115584625B (en) | Organic fiber, fiber composite material, preparation method and application thereof | |
| CN117865510B (en) | Glass fiber reinforced material for wind power blade and preparation method thereof | |
| KR102571546B1 (en) | Composition for fiber-reinforced composite material, fiber-reinforced composite material and molding thereof | |
| WO2017095893A1 (en) | Peroxy ester cure of liquid prepolymer compositions | |
| CN1259355C (en) | Shell-core polymer containing phenolic resin and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071128 Termination date: 20200216 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |