CN102453218A - Preparation method of composite silane coupling agent modified silicon micropowder - Google Patents
Preparation method of composite silane coupling agent modified silicon micropowder Download PDFInfo
- Publication number
- CN102453218A CN102453218A CN201010534501XA CN201010534501A CN102453218A CN 102453218 A CN102453218 A CN 102453218A CN 201010534501X A CN201010534501X A CN 201010534501XA CN 201010534501 A CN201010534501 A CN 201010534501A CN 102453218 A CN102453218 A CN 102453218A
- Authority
- CN
- China
- Prior art keywords
- coupling agent
- polyisobutene
- maleic anhydride
- preparation
- initiator
- 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.)
- Pending
Links
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a coupling agent for filling and modifying an organic polymer and a preparation method thereof. The preparation method comprises the step of carrying out a grafting reaction on maleic anhydride and polyisobutene under the action of an initiator or without the initiator so as to obtain a maleic anhydride grafted polyisobutene polymer, namely the coupling agent, wherein the controllable range of the grafting rate is 1-80%; polyisobutene is common polyisobutene or high-activity polyisobutene with the molecular weight of 800-10000; the grafting reaction temperature is 120-250 DEG C; and the reaction time is 30-240 minutes. The prepared coupling agent can effectively improve the compatibility and the adhesive force of the organic polymer and an inorganic filling material, and has the advantages of no pollution, precise grafting rate control, wide application range and the like.
Description
Technical field
The present invention relates to a kind of maleic anhydride and polyisobutene of utilizing, under the effect of initiator or no initiator, carry out graft polymerization reaction, preparation can be used for the filling-modified maleic anhydride graft polyolefin polymerization compound coupling agent of organic polymer.
Background technology
Have nonpolar and crystalline organic polymer, very poor with other materials like consistencies such as polar polymer, inorganic fillers, can't prepare useful intermingling material.In order to make matrix material reach the performance of expection, need to use coupling agent carry out modification, to strengthen the consistency and the bonding force of it and basic resin to the weighting material surface.Coupling agent is to improve plastic products quality class, raising plastics added value, promotion plastics new product development and The application of new technique to the effect of weighting material interface modification.
Maleic anhydride and polyolefin graft polymers are coupling agent, all are widely used at aspects such as blend polymer, polymer/inorganic weighting material, polymkeric substance/organic fibre, composite reinforcing material and stickers.The method for preparing maleic anhydride and polyolefin graft polymers at present both at home and abroad has scorification, solution method, radiation method and solid phase method, and wherein most important method is a scorification.Fusion-grafting can carry out in single screw extrusion machine, twin screw extruder or Brabender rheometer.For example set forth among the CN123054 with Vestolen PP 7052, maleic anhydride, initiator and other additives; Uniform mixing under the help of paucidisperse agent; Then mixture is added in the forcing machine hopper and melt extrudes, but the product that obtains all exist the maleic anhydride residual quantity high, crosslinked serious, percentage of grafting control is inaccurate, the problem of mobile difference.Though add cross-linked inhibitor through adopting, the method for inhibitor or employing mixed initiator is played a role, and effect is also not obvious.
In high carbon acid calcium filled polypropylene, poly project, requiring calcium carbonate-filled amount is 50%, selects various coupling agents such as titanic acid ester etc. for use, and the loading level of lime carbonate can only reach 30%, and performance index do not reach requirement yet, fails at present to solve always.
Summary of the invention
The objective of the invention is to propose with the technical scheme of maleic anhydride graft polyisobutene polymkeric substance as coupling agent; Make calcium carbonate-filled amount meet and exceed 50%, and adopt that a kind of simple and feasible method obtains that pollution-free (the maleic anhydride residual quantity is very low), degree of crosslinking are low, good fluidity, percentage of grafting control accurate maleic anhydride graft polyisobutene polymkeric substance coupling agent.
The inventive method is that maleic anhydride and polyisobutene are added in the reactor drum of band stirring, and the adding stirring solvent is even, under nitrogen protection, adds initiator or does not add initiator, carries out graft reaction, and temperature of reaction is 120-2500 ℃, successive reaction 30-240 minute.Remove unreacted maleic anhydride with nitrogen gas formulation then, reclaim solvent, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent product at last.
Polyisobutene of the present invention is common polyisobutene or the high-activity polyisobutene of molecular weight 800-10000, and high-activity polyisobutene requires end alkene content greater than 60%, preferred 70-90%.
Solvent of the present invention can be selected benzene,toluene,xylene, ethyl acetate, acetone, butanone, methylethylketone, chloroform, propyl carbinol for use and not have aromatic hydrocarbon solvent.Solvent load is the 10-80% (weight) of polyisobutene amount, preferred 30-50%.
Initiator of the present invention can be selected alkyl peroxide, ester class superoxide and acyl class superoxide for use; Preferably Di Cumyl Peroxide 99, Lucidol, propionic acid acid amides, stearylamide; Tert-butyl peroxide, ditertiary butyl peroxide; Tert-butyl peroxide trimethylacetic acid ester, Diisopropyl azodicarboxylate, 2,3-dimethyl--2,3-diphenyl butane, peroxidized t-butyl perbenzoate.The mixture of one or more materials in optimum Di Cumyl Peroxide 99, Lucidol, ditertiary butyl peroxide, the tert-butyl peroxide valerate.
Temperature of reaction of the present invention is 120-250 ℃, preferred 150-200 ℃.This TR is one of key of the present invention, and temperature of reaction is lower than 120 ℃, and reaction conversion ratio is low; Temperature of reaction is higher than 250 ℃, and maleic anhydride and polyisobutene will speed up decomposition.
Reaction times of the present invention is 30-240 minute, preferred 90-120 minute.
The mol ratio of initiator of the present invention and maleic anhydride is 1: 8-15, preferred 1: 10-12.
The mol ratio of maleic anhydride of the present invention and polyisobutene is 1: 1-8, preferred 1: 3-5.
The maleic anhydride graft polyisobutene polymkeric substance coupling agent of the present invention preparation, its percentage of grafting controlled range be at 1-80%, preferred 2-40%, most preferably 5-20%.
Organic polymer of the present invention can be SE, Vilaterm, Vestolen PP 7052, PS, ethylene-propylene copolymer, ethene-vinyl acetate copolymer, engineering plastics, polyester, nylon, rubber, epoxy resin, resol, insatiable hunger resin.
Weighting material of the present invention can be lime carbonate, glass, talcum, mica, kaolin, silicon-dioxide, titanium oxide, red mud, flyash, zeyssatite, glass microballon, permanent white (calcium), silica powder, the tremolite, aluminum oxide, wollastonite, carbon black, silica-alumina carbon black, brucite.
Maleic anhydride graft polyisobutene polymkeric substance is because its structural characteristics; It is a kind of good long-chain coupling agent that contains side chain; Polyisobutene part in the maleic anhydride graft polyisobutene polymkeric substance is good with the resin compatible of infill system; And can form intermolecular entanglement, carboxylic group and weighting material form complexing or ionic linkage chemical action, help improving the combination between weighting material and the polymeric matrix; Can significantly improve the performance such as tensile strength, shock strength, rigidity, heat-drawn wire, processing fluidity of system, be a kind of new and effective coupling agent.Product is through experimental applications, and calcium carbonate-filled amount meets and exceeds 50%, and each item performance index also reach requirement fully.
Embodiment
Following instance is to further specify of the present invention, rather than limits scope of the present invention.
Embodiment 1-3 is the preparation of high-activity polyisobutene grafted maleic anhydride under the no initiator condition.
Embodiment 1
With 1000 gram end alkene content is that 70% high-activity polyisobutene (molecular weight 2300) adds in the reactor drum of band stirring; Behind nitrogen replacement, add 0.8 maleic anhydride in 1: 5 the ratio of mol ratio of maleic anhydride and polyisobutene, the toluene 300ml mixing that stirs; At speed setting is 600rpm; Temperature of reaction is reaction 200 minutes under 180 ℃ the condition, carries 50 minutes at 190 ℃ with nitrogen gas at last, removes unreacted maleic anhydride; Reclaim solvent xylene, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent.
Prepared reactant is placed vacuum drying oven under 110 ℃ temperature dry 24 hours, removes the maleic anhydride monomer that has neither part nor lot in graft reaction, guarantee in the grafts maybe partly hydrolysed anhydride group be reduced into the form of cyclic anhydride base.From dried reactant, take out the 1-2g sample, be placed in the xylene solution of 150ml and reinforce heat of solution, the NaOH ethanolic soln with 0.1M after 4 hours carries out titration to it, surveys its percentage of grafting.The result sees table 1.
Embodiment 2
With 1000 gram end alkene content is that 71% high-activity polyisobutene (molecular weight 1300) adds in the reactor drum of band stirring; After the nitrogen conversion; 1: 5 ratio of mol ratio in maleic anhydride and polyisobutene adds 1.5 gram maleic anhydrides, YLENE 300ml, and mixing stirs; At speed setting is 600rpm, and temperature of reaction is reaction 200 minutes under 180 ℃ the condition.Remove unreacted maleic anhydride with nitrogen gas formulation, reclaim solvent, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent, adopt with instance 1 identical volumetry and survey its percentage of grafting.The result sees table 1.
Embodiment 3
With 1000 gram alkene content is that 69% high-activity polyisobutene (molecular weight 900) adds in the reactor drum of band stirring; After the nitrogen conversion, in 1: 5 ratio of mol ratio adding, the 2.2 gram maleic anhydrides of maleic anhydride and polyisobutene, benzene 30ml; Mixing stirs; At speed setting is 600rpm, and temperature of reaction is under 180 ℃ the condition, to react 200 minutes.Remove unreacted maleic anhydride with nitrogen gas formulation, reclaim solvent, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent, adopt with instance 1 identical volumetry and survey its percentage of grafting.The result sees table 1.
From table 1, can see, need not initiator for high-activity polyisobutene, just can obtain pollution-free (the maleic anhydride residual quantity is very low), low, the good fluidity of degree of crosslinking, percentage of grafting are controlled accurate maleic anhydride graft polyisobutene polymkeric substance coupling agent.
Embodiment 4-5 is the preparation of common polyisobutene grafted maleic anhydride under the initiator effect.
Embodiment 4
Restrain common polyisobutene (molecular weight 2300) with 1000 and add in the reactor drum of being with stirring, after the nitrogen conversion, in 1: 5 ratio of mol ratio adding, the 0.8 gram maleic anhydride of maleic anhydride and polyisobutene; Acetone 300ml; The mixing that stirs adds section's initiator ditertiary butyl peroxide, is 600rpm at speed setting; Temperature of reaction is under 180 ℃ the condition, to react 200 minutes.Carry 50 minutes at 190 ℃ with nitrogen gas at last, remove unreacted maleic anhydride, reclaim solvent, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent, adopt with instance 1 identical volumetry and survey its percentage of grafting.The result sees table 1.
Embodiment 5
Restrain common polyisobutene (molecular weight 1300) with 1000 and add in the reactor drum of being with stirring, after the nitrogen conversion, in 1: 5 ratio of mol ratio adding, the 1.5 gram maleic anhydrides of maleic anhydride and polyisobutene; Propyl carbinol 300ml; The mixing that stirs adds section's initiator ditertiary butyl peroxide, is 600rpm at speed setting; Temperature of reaction is under 180 ℃ the condition, to react 120 minutes.Nitrogen gas is carried and is removed unreacted maleic anhydride, reclaims solvent, obtains maleic anhydride graft polyisobutene polymkeric substance coupling agent, adopts with instance 1 identical volumetry and surveys its percentage of grafting.The result sees table 1.
From table 1, can see; Common polyisobutene is grafted maleic anhydride under action of evocating; Also can obtain pollution-free (the maleic anhydride residual quantity is very low), low, the good fluidity of degree of crosslinking, percentage of grafting are controlled accurate maleic anhydride graft polyisobutene polymkeric substance coupling agent.
Implement 6-7 and be to utilize maleic anhydride graft polyisobutene polymkeric substance coupling agent that the present invention prepares with calcium carbonate-filled application in the organic polymer.Comparative Examples 1-2 utilizes titanate coupling agent with calcium carbonate-filled application contrast in the organic polymer.
Embodiment 6
Maleic anhydride graft polyisobutene polymkeric substance coupling agent, lime carbonate, Vilaterm 2200J, the inhibitor 168/1076 of the present invention's preparation were pressed 1.5: 30: 68.5: after 0.05 part by weight wt% was composite, in high-speed mixer, high-speed stirring was 3 minutes under the normal temperature; Send in the twin screw extruder again; Processing temperature is 200 ℃, through melt extruding, behind granulation, drying, the compressing tablet; Press GB1040 test tensile property, GB1043 tests impact property.The result sees table 2.
Comparative Examples 1
Coupling agent titanic acid ester, lime carbonate, Vilaterm 2200J, oxidation inhibitor 168/1076 were pressed 1.5: 30: 68.5: after 0.05 part by weight (wt%) is composite; Stirred 3 minutes in the high-speed mixer high speed, send in the twin screw extruder again, processing temperature is 200 ℃; Through melt extruding; Behind granulation, drying, the compressing tablet, press GB1040 test tensile property, GB1043 tests impact property.The result sees table 2.
Embodiment 7
Maleic anhydride graft polyisobutene polymkeric substance coupling agent, lime carbonate, Vilaterm T30S, the inhibitor 168/1076 of the present invention's preparation were pressed 1.5: 30: 68.5: after 0.05 part by weight wt% was composite, in high-speed mixer, high-speed stirring was 3 minutes under the normal temperature; Send in the twin screw extruder again; Processing temperature is 200 ℃, through melt extruding, behind granulation, drying, the compressing tablet; Press GB1040 test tensile property, GB1043 tests impact property.The result sees table 2.
Comparative Examples 2
Coupling agent titanic acid ester, lime carbonate, Vilaterm T30S, inhibitor 168/1076 were pressed 1.5: 30: 68.5: after 0.05 part by weight wt% was composite, in high-speed mixer, high-speed stirring was 3 minutes under the normal temperature; Send in the twin screw extruder again; Processing temperature is 200 ℃, through melt extruding, behind granulation, drying, the compressing tablet; Press GB1040 test tensile property, GB1043 tests impact property.The result sees table 2.
From embodiment 6,7 and Comparative Examples 1,2, can find out; Use maleic anhydride graft polyisobutene polymkeric substance coupling agent to compare with titanate coupling agent, each item indexs such as calcium carbonate-filled rate, elongation at break, tensile strength, shock strength all have significant improvement.
Table 1
Table 2
Claims (10)
1. modification coupling agent and preparation method thereof; It is characterized in that: through maleic anhydride and polyisobutene are added in the reactor drum that stirs; It is even to add stirring solvent; Under nitrogen protection, add initiator or do not add initiator, under 120-250 ℃ of temperature, carried out continuously graft reaction 30-240 minute.Use nitrogen then; Gas is carried; Remove unreacted maleic anhydride and reclaim solvent, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent at last, the mol ratio of maleic anhydride and polyisobutene is 1: 1-8; The mol ratio of initiator and maleic anhydride is 1: 8-15, its percentage of grafting span of control is 1-80%.
2. according to the preparation method of a kind of modification coupling agent described in the claim 1, it is characterized in that polyisobutene is common polyisobutene or the high-activity polyisobutene of molecular weight 800-10000, high-activity polyisobutene requires end alkene content to be not less than 60%.
3. according to the preparation method of a kind of modification coupling agent described in the claim 1; It is characterized in that, solvent can select benzene,toluene,xylene, ethyl acetate, acetone, butanone, methylethylketone, chloroform, propyl carbinol for use and do not have aromatic hydrocarbon solvent, solvent load is the 10-80% (weight) of polyisobutene amount.
4. according to the preparation method of a kind of modification coupling agent described in the claim 1; It is characterized in that: initiator can be selected alkyl peroxide, ester class superoxide and acyl class superoxide for use; Preferred Di Cumyl Peroxide 99, Lucidol, propionic acid acid amides, stearylamide, tert-butyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide trimethylacetic acid ester, Diisopropyl azodicarboxylate, 2; 3-dimethyl--2,3-diphenyl butane, peroxidized t-butyl perbenzoate.The mixture of one or more materials in optimum Di Cumyl Peroxide 99, Lucidol, ditertiary butyl peroxide, the tert-butyl peroxide valerate.
5. according to the preparation method of a kind of modification coupling agent described in the claim 1, it is characterized in that: the mol ratio of maleic anhydride and polyisobutene is 1: 3-5, the mol ratio of initiator and maleic anhydride is 1: 10-12.
6. according to the preparation method of a kind of modification coupling agent described in the claim 1, it is characterized in that: its percentage of grafting span of control of maleic anhydride graft polyisobutene polymkeric substance coupling agent is 5-20%.
7. modification coupling agent is characterized in that: it is method preparation according to claim 1.
8. the purposes of a kind of modification coupling agent described in according to Claim 8, it is characterized in that: it is filling-modified that it is used for organic polymer.
9. the purposes of a kind of modification coupling agent described in according to Claim 8 is characterized in that organic polymer can be SE, Vilaterm, Vestolen PP 7052, PS, ethylene-propylene copolymer, ethene-vinyl acetate copolymer, engineering plastics, polyester, nylon, rubber, epoxy resin, resol, insatiable hunger resin.
10. a kind of purposes with the modification coupling agent described in according to Claim 8, it is characterized in that: weighting material can be lime carbonate, glass, talcum, mica, kaolin, silicon-dioxide, titanium oxide, red mud, flyash, zeyssatite, glass microballon, permanent white (calcium), silica powder, the tremolite, aluminum oxide, wollastonite, carbon black, silica-alumina carbon black, brucite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010534501XA CN102453218A (en) | 2010-10-26 | 2010-10-26 | Preparation method of composite silane coupling agent modified silicon micropowder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010534501XA CN102453218A (en) | 2010-10-26 | 2010-10-26 | Preparation method of composite silane coupling agent modified silicon micropowder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102453218A true CN102453218A (en) | 2012-05-16 |
Family
ID=46036937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010534501XA Pending CN102453218A (en) | 2010-10-26 | 2010-10-26 | Preparation method of composite silane coupling agent modified silicon micropowder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102453218A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788432A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Rubber composition and vulcanized rubber and preparation method thereof and application of vulcanized rubber |
| CN104031336A (en) * | 2012-11-29 | 2014-09-10 | 江苏亨通线缆科技有限公司 | Flame-retardant cable material for communication cable |
| CN104031335A (en) * | 2012-11-29 | 2014-09-10 | 江苏亨通线缆科技有限公司 | Polyvinyl chloride cable sheath material |
| CN104910587A (en) * | 2015-06-16 | 2015-09-16 | 陕西理工学院 | Preparation method for epoxy resin composite material added with modified fly ash |
| CN111100447A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Polyamide-polyester alloy composition and polyamide-6-polybutylene terephthalate alloy |
| CN111440547A (en) * | 2020-04-17 | 2020-07-24 | 科建高分子材料（上海）股份有限公司 | Solar double-glass edge sealing adhesive tape and preparation method thereof |
| CN112280498A (en) * | 2020-10-29 | 2021-01-29 | 杭州福斯特应用材料股份有限公司 | Photovoltaic transparent butyl rubber |
-
2010
- 2010-10-26 CN CN201010534501XA patent/CN102453218A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788432A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Rubber composition and vulcanized rubber and preparation method thereof and application of vulcanized rubber |
| CN103788432B (en) * | 2012-11-01 | 2015-09-16 | 中国石油化工股份有限公司 | The application of rubber combination and vulcanized rubber and preparation method thereof and vulcanized rubber |
| CN104031335B (en) * | 2012-11-29 | 2016-06-29 | 江苏亨通线缆科技有限公司 | Polyvinyl chloride cable material |
| CN104031336A (en) * | 2012-11-29 | 2014-09-10 | 江苏亨通线缆科技有限公司 | Flame-retardant cable material for communication cable |
| CN104031335A (en) * | 2012-11-29 | 2014-09-10 | 江苏亨通线缆科技有限公司 | Polyvinyl chloride cable sheath material |
| CN104031336B (en) * | 2012-11-29 | 2016-06-01 | 江苏亨通线缆科技有限公司 | Flame retardant type data cable cable material |
| CN104910587A (en) * | 2015-06-16 | 2015-09-16 | 陕西理工学院 | Preparation method for epoxy resin composite material added with modified fly ash |
| CN104910587B (en) * | 2015-06-16 | 2016-11-02 | 陕西理工学院 | Add the epoxy resin composite material preparation method of modified coal ash |
| CN111100447A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Polyamide-polyester alloy composition and polyamide-6-polybutylene terephthalate alloy |
| CN111100447B (en) * | 2018-10-26 | 2022-07-12 | 中国石油化工股份有限公司 | Polyamide-polyester alloy composition and polyamide-6-polybutylene terephthalate alloy |
| CN111440547A (en) * | 2020-04-17 | 2020-07-24 | 科建高分子材料（上海）股份有限公司 | Solar double-glass edge sealing adhesive tape and preparation method thereof |
| CN112280498A (en) * | 2020-10-29 | 2021-01-29 | 杭州福斯特应用材料股份有限公司 | Photovoltaic transparent butyl rubber |
| CN112280498B (en) * | 2020-10-29 | 2021-12-31 | 杭州福斯特应用材料股份有限公司 | Photovoltaic transparent butyl rubber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1309751C (en) | Preparation method and application of modified coupling agent | |
| CN102453218A (en) | Preparation method of composite silane coupling agent modified silicon micropowder | |
| CN103073783B (en) | Polypropylene-HMW (high molecular weight)-high density polyethylene-filler blends and preparation method thereof | |
| CN101376683B (en) | Preparation of high melt strength polypropylene | |
| CN102898759B (en) | Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof | |
| CN109593163A (en) | A kind of Polypropylene-based graft object and preparation method thereof | |
| MX2012007201A (en) | Modified polyolefins. | |
| CN101157739A (en) | Method for preparing macromolecule material chain extender | |
| CN101591416B (en) | Environmental-friendly polypropylene compatilizer preparation method | |
| CN1373145A (en) | Method for preparing acid-modified polypropylene resin | |
| CN105859970A (en) | Method for increasing polyolefin grafting efficiency | |
| CN100451056C (en) | Process for preparing predispersed masterbatch of polyolefin and nano calcium carbonate | |
| CN100453574C (en) | Prepn process of grafted ethylene-butylene-dibutyl maleic anhydride copolymer | |
| CN1352655A (en) | Functionalized polypropylenes and process for production | |
| CN101326208A (en) | Coagent-mediated, grafted copolymers and preparation methods | |
| CN101402711B (en) | Method for grafting maleic anhydride with ethylene propylene terpolymer | |
| CN112266592B (en) | High-conductivity nano-mineral modified fully-degradable polymer composite material and preparation method thereof | |
| CN109021583A (en) | Three component tear-proof silicon rubber of one kind and preparation method | |
| CN106032398A (en) | A preparing method of long-chain branched polypropylene | |
| CN102643391B (en) | Ethylene propylene diene monomer grafted maleic anhydride and preparation method thereof | |
| CN100569818C (en) | A kind of method that improves melt strength of polypropylene | |
| CN106279770B (en) | The activated carbon flame retardant of the coupling agent containing composite high-molecular | |
| CN1958634A (en) | Acrylic resin with high bath strength, and preparation method | |
| CN104177793B (en) | PBT (polybutylene terephthalate) toughener as well as preparation method and application thereof | |
| CN1139608C (en) | Mechanochemical method for fusion-grafting vinyl monomer by using polyolefine plastics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120516 |