CN105255411B - The preparation method of organic siloxane modified chlorinated polypropylene adhesive - Google Patents
The preparation method of organic siloxane modified chlorinated polypropylene adhesive Download PDFInfo
- Publication number
- CN105255411B CN105255411B CN201510816273.8A CN201510816273A CN105255411B CN 105255411 B CN105255411 B CN 105255411B CN 201510816273 A CN201510816273 A CN 201510816273A CN 105255411 B CN105255411 B CN 105255411B
- Authority
- CN
- China
- Prior art keywords
- chlorinated polypropylene
- weight
- preparation
- parts
- 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.)
- Expired - Fee Related
Links
Landscapes
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to polymeric material field, and in particular to a kind of preparation method of organic siloxane modified chlorinated polypropylene adhesive.This method uses organosiloxane coupling agent and acrylic ester monomer, and chlorinated polypropylene is modified, comprised the following steps that：A, with organosiloxane coupling agent and acrylic ester monomer prepare grafting solution；B, preparation chlorinated polypropylene solution；C, grafting solution and chlorinated polypropylene solution reaction, isolate and purify reaction product, obtain modified chlorinated polypropylene adhesive.This method preparation technology is simple, it is low to react easily controllable, cost, and grafted chlorinated polypropylene rate is high, and obtained modified chlorinated polypropylene adhesive bonding force and waterproof effect strengthen.
Description
Technical field
The present invention relates to polymeric material field, and in particular to a kind of organic siloxane modified chlorinated polypropylene adhesive
Preparation method.
Background technology
With social development and the increasingly raising of human aesthetic, it is necessary to cover with paint, lacquer, colour wash, etc. polypropylene (PP) material surface, make
It further meets the demand of people in outward appearance and performance.Polypropylene surface coloring is poor, in order to improve paint adhesion, can
Make it that substrate surface is roughening, pole occur using methods such as sided corona treatment, flame treatment, chemical treatment or coating macromolecule priming paint
Property group so that improve it surface can, increase base material and coating adhesive force.However, conventional sided corona treatment, flame treatment
It can be limited with chemical treatment by different degrees of, such as environmental pollution, covering with paint and production cost are high, cover with paint, lacquer, colour wash, etc. time restriction.Cause
This, the method that macromolecule priming paint is preferred raising PP colorings is coated in substrate surface, before PP applications, is first coated one layer and is glued
Agent is connect, coating is coated with, bonding agent can improve the adhesive property between coating and PP, and the method simple and fast is not by the time
Restriction, while PP coating process can be optimized.
Chlorinated polypropylene (CPP) is a kind of polyacrylic chemical modification product, is widely used as polypropylene and is applied with resin base
Adhesion promoter between layer.Chlorinated polypropylene has identical main chain with polypropylene, when CPP is applied over PP surfaces, greatly
Strand mutually tangles, thus with good adhesive force.
Suitable grafted monomers are introduced on chlorinated polypropylene strand by Graft Method, using polar group polarity and
Reactivity, can improve the deficiency in chlorinated polypropylene performance, improve bonding force.Common grafted monomers have anhydride group, hydroxyl
Base group, carboxylic group or acrylic acid groups etc..But current modified product is modified using single group mostly, modified
The caking property and water resistance of product are poor, and many technologies (such as Thermal-printing Technology etc.) need water resistance stronger in the market
Modified chlorinated polypropylene adhesive product, such single modified product can not meet the application requirement of association area.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of modified chlorinated polypropylene adhesive, this method
Grafting rate is high, and the adhesive cementability and water resistance of preparation are preferable.
A kind of preparation method of organic siloxane modified chlorinated polypropylene adhesive, comprises the following steps：
A, preparation grafting solution：
Weigh the parts by weight of acrylic ester monomer 25~35, the parts by weight of organosiloxane coupling agent 1.5~3.0 be dissolved in it is molten
In agent, grafting solution is obtained；
B, preparation chlorinated polypropylene solution：
The parts by weight of chlorinated polypropylene 15~40 are weighed, is dissolved in solvent, obtains chlorinated polypropylene solution；
C, prepare modified chlorinated polypropylene adhesive：
The parts by weight of initiator 0.1~1.5 are weighed, wherein half is added into step together with the additive of 0.1~3.5 parts by weight
In chlorinated polypropylene solution obtained by rapid b, second half initiator is added in the grafting solution obtained by step a；Under an inert gas, will
The grafting solution for adding initiator is added in the chlorinated polypropylene solution for adding initiator, and heating is reacted, and reacts
After the completion of cooling discharging, products therefrom is washed, dry, obtain modified chlorinated polypropylene adhesive；
The solvent is at least one of toluene, dimethylbenzene or butyl acetate, the initiator be benzoyl peroxide,
One kind in cumyl peroxide or azo-bis-isobutyl cyanide, the additive is styrene, dimethyl acetamide, dimethyl Asia
One kind in sulfone or acrylamide.
Wherein, the w/v of acrylic ester monomer and solvent described in step a is 1 ﹕ 2~5, organic silica
The w/v of alkane coupling agent and solvent is 1 ﹕ 2~5；The w/v of chlorinated polypropylene and solvent is described in step b
1 ﹕ 2~5.
Wherein, acrylic ester monomer described in step a is 27.5~32 parts by weight, and organosiloxane coupling agent is 2.0
~2.5 parts by weight；Chlorinated polypropylene described in step b is 20~35 weight；Initiator described in step c is 0.25~1.4 weight
Part is measured, additive is 0.25~3 parts by weight.
Wherein, acrylic ester monomer described in step a and organosiloxane coupling agent weight are than preferably 13~16 ﹕ 1.
Wherein, acrylic ester monomer described in step a is methyl methacrylate, acrylic acid, vinylacetate or third
At least one of olefin(e) acid butyl ester, preferably butyl acrylate.
Wherein, organosiloxane coupling agent described in step a is vinyltrimethoxy silane, (the b- methoxies of vinyl three
Base oxethyl) at least one of silane or γ-methacryloxypropyl trimethoxy silane, preferably γ-methyl-prop
Alkene acryloxypropylethoxysilane trimethoxy silane.
Wherein, initiator described in step c is benzoyl peroxide, and its consumption is chlorinated polypropylene, esters of acrylic acid list
Body and the 2.5% of organosiloxane coupling agent gross mass.
Wherein, reaction temperature described in step c is 80~115 DEG C, preferably 85~100 DEG C；The reaction time be 1~
6h, preferably 2.5~4h.
Wherein, using at least one of methanol, butyl acetate, acetone or methanol in step c.
Wherein, the chlorinated polypropylene is the chlorinated polypropylene of chlorinity 26~45%.
Embodiment
The present invention provides the preparation side of the modified chlorinated polypropylene adhesive of a kind of high grafting rate, cementability and water-tolerant
Method, comprises the following steps：
A, preparation grafting solution：
Weigh the parts by weight of acrylic ester monomer 25~35, the parts by weight of organosiloxane coupling agent 1.5~3.0 be dissolved in it is molten
In agent, grafting solution is obtained；
B, preparation chlorinated polypropylene solution：
The parts by weight of chlorinated polypropylene 15~40 are weighed, is dissolved in solvent, obtains chlorinated polypropylene solution；
C, prepare modified chlorinated polypropylene adhesive：
The parts by weight of initiator 0.1~1.5 are weighed, wherein half is added into step together with the additive of 0.1~3.5 parts by weight
In chlorinated polypropylene solution obtained by rapid b, second half initiator is added in the grafting solution obtained by step a；Under an inert gas, will
The grafting solution for adding initiator is added in the chlorinated polypropylene solution for adding initiator, and heating is reacted, and reacts
After the completion of cooling discharging, products therefrom is washed, dry, obtain modified chlorinated polypropylene adhesive；
The solvent is at least one of toluene, dimethylbenzene or butyl acetate, the initiator be benzoyl peroxide,
One kind in cumyl peroxide or azo-bis-isobutyl cyanide, the additive is styrene, dimethyl acetamide, dimethyl Asia
One kind in sulfone or acrylamide.
Wherein, the w/v of acrylic ester monomer and solvent described in step a is 1 ﹕ 2~5, organic silica
The w/v of alkane coupling agent and solvent is 1 ﹕ 2~5；The w/v of chlorinated polypropylene and solvent is described in step b
1 ﹕ 2~5.
Wherein, acrylic ester monomer described in step a is 27.5~32 parts by weight, and organosiloxane coupling agent is 2.0
~2.5 parts by weight；Chlorinated polypropylene described in step b is 20~35 weight；Initiator described in step c is 0.25~1.4 weight
Part is measured, additive is 0.25~3 parts by weight.
Wherein, acrylic ester monomer described in step a and organosiloxane coupling agent weight are than preferably 13~16 ﹕ 1.
Wherein, acrylic ester monomer described in step a is methyl methacrylate, acrylic acid, vinylacetate or third
At least one of olefin(e) acid butyl ester, preferably butyl acrylate, the organosiloxane coupling agent are vinyl trimethoxy silicon
At least one in alkane, (b- methoxy ethoxies) silane of vinyl three or γ-methacryloxypropyl trimethoxy silane
Plant, preferably γ-methacryloxypropyl trimethoxy silane.
Wherein, the chlorinated polypropylene is the chlorine of the chlorinated polypropylene, preferably chlorinity 30% of chlorinity 26~45%
Change polypropylene.When dissolving chlorinated polypropylene in step b, in order to strengthen dissolving and reaction effect, the preferred nitrogen of inert gas, in nitrogen
Condensation is opened under the protective effect of gas, warming while stirring is warming up to 60~80 DEG C of constant temperature again, is completely dissolved chlorinated polypropylene.
Initiator meeting accelerated decomposition under aerobic and Elevated Temperature Conditions, silicone coupling agents can hydrolyze to form crosslinking production under water environment
Thing, it is to start to be passed through nitrogen that both of which, which is unfavorable in the progress of reaction, the present invention in step b, and step c is also at the protection of nitrogen
Under, it is ensured that reaction is smoothed out.It is preferred that, it can be repeated for step a after solvent condensation in step b.
Wherein, initiator is preferably benzoyl peroxide described in step c, and its consumption is chlorinated polypropylene, acrylate
Class monomer and the 2.5% of organosiloxane coupling agent gross mass.
Initiator BP can be decomposed for a long time under initiation temperature, cause to trigger effect to decline, it is necessary to follow-up logical
Cross and add initiator to lift initiation effect.In step c of the present invention when preparing modified chlorinated polypropylene adhesive, initiator point
The grafting solution obtained by step a is not added to, is triggered in the chlorinated polypropylene solution obtained by step b, it is to avoid initiator
Decomposition, reduce the consumption of initiator；Meanwhile, carrying for product graft rate is also contributed to by way of being added separately to initiator
It is high；In addition, the use of additive further enhancing the effect of initiator, reduce preferred in the consumption of initiator, the present invention
Additive is acrylamide.
Wherein, reaction temperature described in step c is 80~115 DEG C, preferably 85~100 DEG C；The reaction time be 1~
6h, preferably 2.5~4h.The reaction being substantially carried out in step c is：
In formula：A replaced for used acrylic ester monomer or organosiloxane coupling agent class monomer.
It is preferred that, by resulting graft modification chlorinated polypropylene product when being washed in step c, slowly pour into methanol,
Stand after 8~24h, the clear liquid inclined above, the butyl acetate for then adding 10~50ml dissolves sediment in a heated condition,
Then the sediment that butyl acetate dissolves slowly is poured into methanol again, be iteratively repeated 3~6 times, finally by the precipitation of gained
(weight compares 1 for thing acetone and methyl alcohol mixed liquor：10~20) carry out cyclic washing 3~6 times；Drying mode is using baking in step c
It is dry.
Beneficial effects of the present invention：
1st, the present invention introduces organosiloxane coupling agent on chlorinated polypropylene side chain, by acrylic ester monomer and
Silicone coupling agents change altogether, and obtained adhesive has stronger than single esters of acrylic acid modified chlorinated polypropylene adhesive
Cohesive force and more excellent waterproof effect, can be widely applied for the bonding of the non-polar polymers such as polypropylene, polyethylene.
2nd, added present invention introduces the stronger styrene of polarity, dimethyl acetamide, dimethyl sulfoxide (DMSO) or acrylamide
Agent, effectively lifts grafting rate, and the raising of grafting rate further improves cohesive force and waterproof effect.
3rd, raw material of the present invention is easy to get, preparation technology is simple, it is easily controllable to react, and solvent is repeatable to be utilized, changes initiator
Adding method also reduces initiator amount, reduce further cost.
The embodiment of the present invention is described further below by embodiment, but not therefore by the present invention
Protection domain limitation in one embodiment.
Embodiment 1
A, grafting solution preparation
By weight methyl methacrylate：Vinyltrimethoxy silane=parts by weight the methyl of 13 ﹕, 1 precises 27.5
Methyl acrylate, 2.5 parts by weight of ethylene base trimethoxy silanes measure 100ml butyl acetates in beaker, accurately and pour into beaker
In, stirring to methyl methacrylate and vinyltrimethoxy silane is dissolved completely, and grafting solution is made；
B, preparation chlorinated polypropylene solution：
By 20 parts by weight chlorinated polypropylenes and 100ml butyl acetates, four mouthfuls of burnings with condensation and logical nitrogen device are added to
In bottle, stir and be passed through nitrogen, under nitrogen protective condition, open condensation, heat up, temperature is warming up to 60~80 DEG C of constant temperature again, stirred
Mix 0.5~3 hour, chlorinated polypropylene is all dissolved, chlorinated polypropylene solution is made；
C, prepare modified chlorinated polypropylene adhesive：
The parts by weight initiator B PO of precise 0.25, half therein is added to the grafting liquid configured in a steps
In, grafting liquid is added to standby in constant pressure buret.Then second half initiator weighed up is dissolved with 10ml butyl acetates again,
0.25 parts by weight propylene acid amides is weighed in addition, is added to together in chlorinated polypropylene solution solvent in b step, in blanket of nitrogen
Under, temperature is warming up to reflux temperature and carries out initiation reaction.The grafting liquid being added dropwise in constant pressure funnel is started simultaneously at, control exists
After completion of dropping in 1~2 hour, completion of dropping, then after isothermal reaction 2.5 hours, stop reaction, cooling discharging, by what is obtained
Product is slowly poured into methanol, is stood after 8h, the clear liquid inclined above, then adds 40ml butyl acetate in a heated condition
Sediment is dissolved, then the sediment that butyl acetate dissolves slowly is poured into methanol again, is iteratively repeated 3 times, finally by institute
The sediment obtained carries out cyclic washing 3 times with acetone and methanol.
Embodiment 2~5, comparative example 6
Embodiment 2~5, comparative example 6 are in addition to different described in table 1 below, rest materials and the equal phase of be the same as Example 1 of reaction condition
Together.
The reaction substrate of table 1, content (parts by weight) and condition
Raw materials used chlorinated polypropylene, methyl methacrylate, butyl acrylate, third in embodiment 1~5 and comparative example 6
Olefin(e) acid, vinyltrimethoxy silane, (b- methoxy ethoxies) silane of vinyl three and γ-methacryloxypropyl three
Methoxy silane is technical pure, toluene, acetone, butyl acetate, methanol, styrene, dimethyl acetamide, dimethyl sulfoxide (DMSO),
Acrylamide, benzoyl peroxide, cumyl peroxide and azo-bis-isobutyl cyanide are that analysis is pure, and above-mentioned each raw material comes extremely
Commercial products.Wherein, chlorinated polypropylene is the chlorinated polypropylene of chlorinity 30%.
The modified chlorinated polypropylene adhesive of embodiment 1~5 and the gained of comparative example 6 is determined into adhesive force, water resistance respectively
And grafting rate.
Adhesive force test is carried out using paint film lattice drawing method, is taken PP, PVC, PE sample board of clean surface flat smooth, is used
Isopropanol (IPA) cleans plastic front board, and wiping is dried stand-by.By gained adhesive and chloroform by weight the wiring solution-formings of 1 ﹕ 10,
Take equivalent solution to drop on sample board respectively, in being bakeed 30 minutes or so at 80 DEG C, treat that solvent volatilizees completely, coating will be completed
Panel stands 3 days at room temperature, and its effect is tested.Coating is done into lattice battle array pattern cut with cross-cut tester and penetrated, is carried out
Divide and count its adhesive force size.
Water resistance test is according to national standard《The paint film water resistance determination methods of GB/T1733-93》Carry out.After film
PP plates, paraffin and rosin blend with weight than 1 ﹕ 1 seal its edge, to prevent edge from soaking, afterwards below PP plates
Half is placed in distilled water, observes whether film bubbles discoloration at regular intervals, when film occurs when foaming changes colour
Write down soak time.
Properties of product measurement result made from embodiment 1~5 and comparative example 6 is as shown in table 2：
The modified chlorinated polypropylene adhesive performance measurement result of table 2
As described in Table 2, comparative example 6 is modified using single butyl acrylate, and caking property and water resistance are poor, embodiment
1~5 utilizes acrylic ester monomer and organosiloxane coupling agent to chlorinated polypropylene modified, prepared adhesive bonds
It is preferable with water resistance, while further increasing grafting rate.
The method of what the present invention was provided prepare modified chlorinated polypropylene adhesive improves the grafting rate of chlorinated polypropylene, this
Method is simple to operate, and raw material is easy to get, and obtained adhesive has stronger cohesive force and preferably waterproof effect, can be widely applied for
The bonding of the non-polar polymers such as polypropylene, polyethylene.
Claims (7)
1. a kind of preparation method of organic siloxane modified chlorinated polypropylene adhesive, comprises the following steps：
A, preparation grafting solution：
Weigh the parts by weight of at least one of methyl methacrylate, acrylic acid, vinylacetate or butyl acrylate 25~35,
The parts by weight of organosiloxane coupling agent 1.5~3.0 are dissolved in solvent, obtain grafting solution；The organosiloxane coupling agent
For vinyltrimethoxy silane, (b- methoxy ethoxies) silane of vinyl three or γ-methacryloxypropyl front three
At least one of TMOS；
B, preparation chlorinated polypropylene solution：
The parts by weight of chlorinated polypropylene 15~40 are weighed, is dissolved in solvent, obtains chlorinated polypropylene solution；
C, prepare modified chlorinated polypropylene adhesive：
The parts by weight of initiator 0.1~1.5 are weighed, wherein half is added into step b together with the additive of 0.1~3.5 parts by weight
In gained chlorinated polypropylene solution, second half initiator is added in the grafting solution obtained by step a；Under an inert gas, it will add
The grafting solution for having entered initiator is added in the chlorinated polypropylene solution for adding initiator, and heating is reacted, and has been reacted
Into rear cooling discharging, products therefrom is washed, dried, modified chlorinated polypropylene adhesive is obtained；
The solvent is at least one of toluene, dimethylbenzene or butyl acetate, and the initiator is benzoyl peroxide, peroxide
Change one kind in diisopropylbenzene (DIPB) or azodiisobutyronitrile, the additive be styrene, dimethyl acetamide, dimethyl sulfoxide (DMSO) or
One kind in acrylamide.
2. the preparation method of organic siloxane modified chlorinated polypropylene adhesive according to claim 1, it is characterised in that：
At least one of methyl methacrylate, acrylic acid, vinylacetate or butyl acrylate described in step a are 27.5
~32 parts by weight, organosiloxane coupling agent is 2.0~2.5 parts by weight；
Chlorinated polypropylene described in step b is 20~35 weight；
Initiator described in step c is 0.25~1.4 parts by weight, and additive is 0.25~3 parts by weight.
3. the preparation method of organic siloxane modified chlorinated polypropylene adhesive according to claim 1, it is characterised in that：
At least one of methyl methacrylate, acrylic acid, vinylacetate or butyl acrylate described in step a and organic silica
Alkane coupling agent weight ratio is 13~16 ﹕ 1.
4. the preparation method of organic siloxane modified chlorinated polypropylene adhesive according to claim 1, it is characterised in that：
Initiator described in step c is benzoyl peroxide, and its consumption is chlorinated polypropylene, methyl methacrylate, acrylic acid, acetic acid
At least one of vinyl acetate or butyl acrylate and the 2.5% of organosiloxane coupling agent gross mass.
5. the preparation method of the organic siloxane modified chlorinated polypropylene adhesive according to any one of Claims 1 to 4, its
It is characterised by：Reaction temperature described in step c is 80~115 DEG C, and the reaction time is 1~6h.
6. the preparation method of organic siloxane modified chlorinated polypropylene adhesive according to claim 1, it is characterised in that：
Washing process is using at least one of methanol, butyl acetate, acetone or methanol in step d.
7. the preparation side of the organic siloxane modified chlorinated polypropylene adhesive according to Claims 1 to 4 or 6 any one
Method, it is characterised in that：The chlorinated polypropylene is the chlorinated polypropylene of chlorinity 26~45%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510816273.8A CN105255411B (en) | 2015-11-20 | 2015-11-20 | The preparation method of organic siloxane modified chlorinated polypropylene adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510816273.8A CN105255411B (en) | 2015-11-20 | 2015-11-20 | The preparation method of organic siloxane modified chlorinated polypropylene adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105255411A CN105255411A (en) | 2016-01-20 |
| CN105255411B true CN105255411B (en) | 2017-09-19 |
Family
ID=55095352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510816273.8A Expired - Fee Related CN105255411B (en) | 2015-11-20 | 2015-11-20 | The preparation method of organic siloxane modified chlorinated polypropylene adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105255411B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106075873A (en) * | 2016-08-19 | 2016-11-09 | 哈尔滨体育学院 | A kind of modified fibre strengthens the preparation method of skis |
| CN110423309A (en) * | 2019-07-17 | 2019-11-08 | 广州市荔威化工有限公司 | A kind of preparation method of the acrylate modified chlorinated polypropylene of environment-friendly type aqueous organosiloxane |
| CN112679667B (en) * | 2020-12-09 | 2022-08-02 | 沧州师范学院 | Flexible polymer needle containing siloxane group and preparation method and application thereof |
| CN113480954A (en) * | 2021-07-27 | 2021-10-08 | 中山市皇冠胶粘制品有限公司 | Graft-modified acrylate pressure-sensitive adhesive, double-sided adhesive tape, and preparation method and application thereof |
| CN113667419B (en) * | 2021-08-12 | 2023-04-28 | 烟台正海合泰科技股份有限公司 | Three-layer adhesive film and production method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260178B (en) * | 2008-02-22 | 2010-12-15 | 常州南京大学高新技术研究院 | Modified chlorinated polyolefin resin and preparing method thereof |
-
2015
- 2015-11-20 CN CN201510816273.8A patent/CN105255411B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105255411A (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105255411B (en) | The preparation method of organic siloxane modified chlorinated polypropylene adhesive | |
| CN104422979B (en) | Polarizing coating, laminated body and image display device with transparent conductive film adhesive phase | |
| CN102504733B (en) | Water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive and polyethylene protective film | |
| CN104672403A (en) | Environment-friendly silicon-acrylate emulsion and preparation method thereof | |
| CN107699095A (en) | Coating composition | |
| CN109021851B (en) | A kind of acrylic protective film and preparation method thereof | |
| CN105348433B (en) | The good water-based plastic cement acrylic resin of wearability, alcohol resistance | |
| TW201241011A (en) | Composition | |
| CN104497332B (en) | A kind of mould release membrance and preparation method thereof | |
| CN106543877A (en) | The modified polyurethane woodwork coating of water polyacrylic acid containing organosilicon and its preparation method and application | |
| CN103951789B (en) | A kind of resistant to elevated temperatures minute surface silver resin and preparation method thereof | |
| Chen et al. | Preparation and characterization of polyacrylate/polymerized rosin composite emulsions by seeded semicontinuous emulsion polymerization | |
| CN108641559A (en) | A kind of expanding fire retardant and its preparation method and application | |
| CN104530996B (en) | LCD release film and production method thereof | |
| CN101974118A (en) | Solvent thermal polymerization method of styrene-silane copolymer | |
| CN104592848B (en) | BOPET release film and preparation method thereof | |
| CN104974307B (en) | Inorganic silicon maleic anhydride grafted polyethylene alcohol material and preparation method and application | |
| JP6409005B2 (en) | Use of flowable polymer composition to seal photovoltaic module | |
| JP2002212241A (en) | Graft polyolefin and resin composition for coating containing the same | |
| CN109337085A (en) | A kind of synthesis of the silicon oil modified styrene maleic anhydride copolymer of Amino End Group | |
| CN111225948B (en) | Modified polyolefin resin composition and method for producing the same | |
| CN115141326B (en) | Modified wax powder and preparation method and application thereof | |
| US20070059546A1 (en) | One solution-type thermosetting compositions for color filter protective films and color filters using the same | |
| CN106244094A (en) | A kind of dual composition addition type silicone rubber of bonding woven dacron base material and preparation method thereof | |
| TWI510511B (en) | Polymer, preparation method thereof, composition and film comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170919 Termination date: 20191120 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |