CN110396160A - A kind of novel acrylic modified rubber foam resin and preparation method thereof - Google Patents
A kind of novel acrylic modified rubber foam resin and preparation method thereof Download PDFInfo
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- CN110396160A CN110396160A CN201910724768.6A CN201910724768A CN110396160A CN 110396160 A CN110396160 A CN 110396160A CN 201910724768 A CN201910724768 A CN 201910724768A CN 110396160 A CN110396160 A CN 110396160A
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- foam resin
- acrylic modified
- foam
- modified rubber
- rubber foam
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/08—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of nitriles
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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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a kind of novel acrylic modified rubber foam resins and preparation method thereof, combine the elastomeric feature of rubber, so that resin itself has buffering vibration-absorbing function well, in addition response type acrylic monomer has been introduced again, the crosslinking degree for greatly increasing rubber in this way has higher cohesive strength compared with acrylic foam；Meanwhile and substantially increase the binding force of foam itself with acrylic acid adhesive, there is better interface binding power compared with PU foam, in summary described two advantages, so that the impact resistance of final foam has better promotion.
Description
Technical field
The invention belongs to jointing material technical field, it is related to a kind of novel acrylic modified rubber foam resin and its system
Preparation Method.
Background technique
Foam as a kind of special functional material, by own have it is light, spring back, thickness range is wide and
A series of features such as moderate cost, so that being all widely used in current many electronic products, and at present in addition to tradition
PE foam outside, and occur many novel foams simultaneously, such as acrylic foam, PU foam.The above foam is when in use
Mainly foam one side or two sides coating adhesive be made adhesive tape be mainly used for using, basic application mobile phone,
The screen frame of pad is sealing adhesive, and there are also the bondings for cell phone rear cover.Main effect is in addition to filling up the same of thickness difference
When, but also with waterproof, closed and cushion performance, it is PE foam that usage amount is maximum at present, because cost is relatively low for it, technique at
Ripe and can meet use for general performance requirement, this foam is mainly to be filled with using the alkene dissolved by high pressure
Then inert gas again vacuumize foaming, in addition to this, more advanced for IXPE at present, i.e., by polyethylene or modification
Polyethylene and various filler extrusion moldings, by electron accelerator crosslinking with radiation (without chemical bridging agent), height is made in high temperature foaming
Polymeric foam material, it is netted that this foam pattern forms the chemistry key connection between long linear molecule by certain forms
Structure is greatly improved on more traditional PE foam cohesive force, but this cohesive force is still insufficiently resistant to high intensity
Impact.But with mobile phone constantly narrow and slimming, existing a variety of PE foams are just difficult again while more than satisfaction
Three performances are based on this, and acrylic foam, PU (polyurethane) foam occur, both foams be with corresponding acrylic,
PU resin, both foams greatly improve the pliability of foam itself, so that foam has good resilience, it is this good
Can deformation restorability, foam can be allowed greatly to be absorbed into when by external impacts by the deformation of strand
Part energy, foam is again resilient after external force disappearance, may make the impact resistance of foam itself in this way
To being promoted, by heat foamable technology, to reach the foam effect of low-density, high rebound, both novel foams are in performance
There is certain promotion compared with PE foam, it is particularly evident especially in shock resistance, but the polymerization of acrylic foam itself
Object Tg is lower, so cohesive force is weaker, in high-intensitive external impacts, foam itself can lead to strand since deformation is excessive
Fracture, so being difficult so that the foam has very strong impact resistance；And PU foam polymer itself is made of soft and hard segments, deformation
Generation realize that hard section can promote the cohesive force of polymer again mainly by soft segment, be to belong to compare from anti-impact force
Outstanding structure, but PU material itself and the compatibility of other materials are poor, so that after two sides is coated with adhesive, often boundary
Intensity at face is poor, and when by external impacts, the glue-line on two sides and the interface of foamed cotton layer are easily separated, to influence
To final shock resistance effect.
Change therefore, it is necessary to seek the novel acrylic that a kind of impact resistance, intensity is good, compatibility is good, is not readily separated
Property rubber foam resin.
Summary of the invention
It is an object of the invention to invent a kind of novel acrylic modified rubber foam resin and preparation method, in solution
State technical problem.
The technical solution adopted by the present invention to solve the technical problems is: providing a kind of novel acrylic modified rubber foam
With resin, raw material summation is 100 benchmark parts, has the following raw material: monomer 16.7%-28.8% according to mass percent meter；Draw
Send out agent 0.1%-0.2%；Antioxidant 0.3%-0.8%；Curing agent is 0.5%-0.8%, and surplus is rubber particles.
As a preferred embodiment of the invention, the monomer is butyl acrylate, hydroxy-ethyl acrylate, propylene
Acid, ethyl acrylate, any one or more in Isooctyl acrylate monomer.
As a preferred embodiment of the invention, shared mass percent includes: propylene to the monomer in the feed
Acid butyl ester 15%-25%, hydroxy-ethyl acrylate 1.5%-3%, acrylic acid 0.2%-0.8%.
As a preferred embodiment of the invention, the initiator is any one or two kinds in BPO or AIBN.
As a preferred embodiment of the invention, the antioxidant is β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid n-octadecyl alcohol ester, any one in four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
Or two kinds.
As a preferred embodiment of the invention, the curing agent is toluene di-isocyanate(TDI) and trimethylolpropane
Addition product, toluene diisocyanate trimer, hexamethylene diisocyanate trimer, hexamethylene diisocyanate poly
Any one or more in body.
As a preferred embodiment of the invention, the rubber particles include that styrene-isoprene-phenylethene is embedding
Section copolymer, Styrene-Butadiene-Styrene Block Copolymer, Hydrogenated SBS, any one or more synthesis in polyacrylonitrile
Rubber.
Another technical solution adopted by the present invention to solve the technical problem thereof is that: a kind of novel acrylic modified rubber is provided
The preparation method of foam resin, comprising steps of
(1) dissolution point under conditions of temperature is 30-60 DEG C after mixing rubber particles and ethyl acetate, toluene sufficiently
It dissipates, obtains mixed liquor；
(2) under conditions of temperature is 40 DEG C, monomer is added in Xiang Suoshu mixed liquor, obtains reaction solution；
(3) nitrogen deoxygenation 0.8-1.5H is filled in Xiang Suoshu reaction solution；
(4) after being warming up to 65 DEG C -85 DEG C, initiator is added；
(5) 2-3.5H is reacted under conditions of temperature is 65 DEG C -85 DEG C, increases viscosity, then proceed to reaction 20min-
40min；
(6) antioxidant is added, then cooling terminates reaction, obtains novel acrylic modified rubber foam resin.
The beneficial effects of the present invention are: present invention employs the excellent rubber resins of resilience as foam main body, in addition
It is modified with acrylic monomer again, so that the compatibility of itself and other materials gets a promotion, while introducing again can
Reactive group, so that foamed cotton layer and the glue-line on two sides have certain reactable, to greatly improve foam resin itself
Shock resistance.In addition to this, when preparing foam, need to introduce heat foamable particle, by heat foamable technology, in foamed cotton layer
It is embedded in the tiny balloon of certain amount, these microballoons have elasticity well, the process restored under external force by deformation
Shock resistance is greatly enhanced to realize.
Specific embodiment
Novel acrylic modified rubber foam resin prepared by the present invention, each raw material component used is respectively: monomer
16.7%-28.8%；Initiator 0.1%-0.2%；Antioxidant 0.3%-0.8%, curing agent L-45E are 0.5%-0.8%；
Surplus is rubber particles；
In above-mentioned formula, monomer selects butyl acrylate (BA), hydroxy-ethyl acrylate (HEA), acrylic acid (AA), in addition
It further include the acrylic monomers such as ethyl acrylate (EA), Isooctyl acrylate monomer (EHA)；Initiator includes BPO, AIBN；Solidification
Curing agent used by agent has the addition product of toluene di-isocyanate(TDI) (TDI) Yu trimethylolpropane (TMP)；Toluene diisocynate
Ester (TDI) tripolymer；Hexamethylene diisocyanate (HDI) tripolymer；Hexamethylene diisocyanate (HDI) polymer etc. is more
Isocyanates curing agent；Antioxidant has β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester (antioxidant
1076), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010)；Rubber particles include
SIS (styrene-isoprene-styrene block copolymer), SBS (Styrene-Butadiene-Styrene Block Copolymer),
The synthetic rubber such as SEBS (Hydrogenated SBS), polyacrylonitrile.
The preparation process of above-mentioned formula are as follows: in temperature be 30-60 after mixing rubber particles and ethyl acetate, toluene sufficiently
Dispersion is dissolved under conditions of DEG C, obtains mixed liquor；Under conditions of temperature is 40 DEG C, monomer is added in Xiang Suoshu mixed liquor, obtains
Obtain reaction solution；Nitrogen deoxygenation 1h is filled with into the reaction solution；After being warming up to 65 DEG C -85 DEG C, initiator is added；It is 65 in temperature
2h is reacted under conditions of DEG C -85 DEG C, increases viscosity, then proceedes to reaction 20min-40min；Antioxidant is added, then drops
Temperature terminates reaction, obtains novel acrylic modified rubber foam resin.
Below in conjunction with specific embodiment, the present invention is further illustrated, but the scope of the present invention is not limited to these
Embodiment.
Raw materials used source is as follows in embodiments:
| Material name | Supplier |
| D1111 | Loose river chemistry Wuxi Co., Ltd |
| D1116 | Loose river chemistry Wuxi Co., Ltd |
| D1160 | Loose river chemistry Wuxi Co., Ltd |
| Butyl acrylate | Zhejiang Satellite Petrochemical Co., Ltd. |
| Hydroxy-ethyl acrylate | Xinghe (Shanghai) trade Co., Ltd |
| Acrylic acid | Zhejiang Satellite Petrochemical Co., Ltd. |
| BPO-75 | Shanghai Jun Sheng trade Co., Ltd |
| Toluene | Suzhou City Asia-Pacific glass for chemical equipment-building Instrument Ltd. |
| Ethyl acetate | Suzhou City Asia-Pacific glass for chemical equipment-building Instrument Ltd. |
Embodiment 1
D1111 rubber particles 200g is accurately weighed, is poured into 2L reaction flask, then weighs toluene (TO) and acetic acid second respectively
Each 603g and 80g of ester (ETAC), is poured into the reaction flask equipped with rubber particles, and dissolution then is sufficiently stirred at 40 DEG C again.To rubber
Micelle is completely dissolved and then is weighed into respectively into reaction flask respectively butyl acrylate, hydroxy-ethyl acrylate and acrylic acid
Then 67.5g, 7.9g and 2.1g are further continued for the stirring 30min at 40 DEG C and are sufficiently mixed above-mentioned raw materials；When the mixing of each raw material is equal
Even and then into reaction flask with 0.5L/min speed is passed through the abundant deoxygenation 1H of nitrogen, and deoxygenation is warming up to 80 again after finishing
DEG C, the initiator B PO (75%) of 0.52g is added in 80 DEG C of backward reaction flask (note: is added with the dissolution of 28g toluene when temperature reaches
Enter, while paying attention to airtightness).The reaction was continued 2H or so at 80 DEG C is added after initiator, to reacting after viscosity significantly increases,
It is further continued for reaction 30min, antioxidant 2.1g (note: being added with the dissolution of 28g toluene) is then added into reaction flask, while with cool
Water cooling stops reacting, and takes out completely reacted glue when temperature drops to 30 DEG C, measures viscosity and solid containing for use, is using
When be added 9.7g isocyanate curing agent L-45E be coated solidification.
Embodiment 2
D1116 rubber particles 173g is accurately weighed, is poured into 2L reaction flask, then weighs toluene (TO) and acetic acid second respectively
Each 603g and 80g of ester (ETAC), is poured into the reaction flask equipped with rubber particles, and dissolution then is sufficiently stirred at 40 DEG C again.To rubber
Micelle is completely dissolved and then is weighed into respectively into reaction flask respectively butyl acrylate, hydroxy-ethyl acrylate and acrylic acid
Then 40.5g, 3.96g and 0.6g are further continued for the stirring 30min at 40 DEG C and are sufficiently mixed above-mentioned raw materials；When each raw material mixes
Uniformly and then the speed into reaction flask with 0.5L/min is passed through the abundant deoxygenation 1H of nitrogen, and deoxygenation is warming up to again after finishing
80 DEG C, when initiator B PO (the 75%) (note: with the dissolution of 28g toluene that 0.27g is added in the backward reaction flask that temperature reaches 80 DEG C
It is added, while paying attention to airtightness).The reaction was continued 2H or so at 80 DEG C is added after initiator, is significantly increased to viscosity is reacted
Afterwards, it is further continued for reaction 30min, antioxidant 0.9g (note: being added with the dissolution of 28g toluene) is then added into reaction flask, simultaneously
Cooled down with cold water and stop reaction, take out completely reacted glue when temperature drops to 30 DEG C, measures viscosity and solid containing stand-by, In
7.6g isocyanate curing agent L-45E is added when use and is coated solidification.
Embodiment 3
D1160 rubber particles 200g is accurately weighed, is poured into 2L reaction flask, then weighs toluene (TO) and acetic acid second respectively
Each 603g and 80g of ester (ETAC), is poured into the reaction flask equipped with rubber particles, and dissolution then is sufficiently stirred at 40 DEG C again.To rubber
Micelle is completely dissolved and then is weighed into respectively into reaction flask respectively butyl acrylate, hydroxy-ethyl acrylate and acrylic acid
Then 54g, 7g and 1.4g are further continued for the stirring 30min at 40 DEG C and are sufficiently mixed above-mentioned raw materials；When each raw material is uniformly mixed it
Afterwards, then the speed into reaction flask with 0.5L/min is passed through the abundant deoxygenation 1H of nitrogen, and deoxygenation is warming up to 80 DEG C after finishing again, when
The initiator B PO (75%) that 0.35g is added in the backward reaction flask of 80 DEG C of temperature arrival (note: is added, together with the dissolution of 28g toluene
When pay attention to airtightness).The reaction was continued 2H or so at 80 DEG C is added after initiator, to reacting after viscosity significantly increases, followed by
Then antioxidant 1.5g (note: being added with the dissolution of 28g toluene) is added into reaction flask, while being dropped with cold water by continuous reaction 30min
Temperature stops reaction, takes out completely reacted glue when temperature drops to 30 DEG C, measures viscosity and solid containing stand-by, when in use plus
Enter 8.3g isocyanate curing agent L-45E and is coated solidification.
Each embodiment of table 1 test knot is as follows:
In conclusion novel acrylic modified rubber foam resin of the present invention and preparation method thereof, combines
In addition the elastomeric feature of rubber has introduced response type propylene so that resin itself has buffering vibration-absorbing function well again
Acrylic monomer greatly increases the crosslinking degree of rubber in this way, has higher cohesive strength compared with acrylic foam；Meanwhile again
The binding force for substantially increasing foam itself with acrylic acid adhesive has a better interface binding power compared with PU foam, it is comprehensive with
Upper described two advantages, so that the impact resistance of final foam has better promotion.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (8)
1. a kind of novel acrylic modified rubber foam resin, which is characterized in that raw material summation is 100 benchmark parts, according to matter
Measuring percentages has the following raw material:
Monomer 16.7%-28.8%；
Initiator 0.1%-0.2%；
Antioxidant 0.3%-0.8%；
Curing agent is 0.5%-0.8%,
Surplus is rubber particles.
2. a kind of novel acrylic modified rubber foam resin according to claim 1, it is characterised in that: the monomer
For any one or more in butyl acrylate, hydroxy-ethyl acrylate, acrylic acid, ethyl acrylate, Isooctyl acrylate monomer.
3. a kind of novel acrylic modified rubber foam resin according to claim 2, it is characterised in that: the monomer
Shared mass percent includes: butyl acrylate 15%-25%, hydroxy-ethyl acrylate 1.5%-3%, acrylic acid 0.2%- in the feed
0.8%。
4. a kind of novel acrylic modified rubber foam resin according to claim 1, it is characterised in that: the initiation
Agent is any one or two kinds in BPO or AIBN.
5. a kind of novel acrylic modified rubber foam resin according to claim 1, it is characterised in that: the antioxygen
Agent is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] any one or two kinds in pentaerythritol ester.
6. a kind of novel acrylic modified rubber foam resin according to claim 1, it is characterised in that: the solidification
Agent is addition product, toluene diisocyanate trimer, two isocyanide of hexa-methylene of toluene di-isocyanate(TDI) and trimethylolpropane
Any one or more in acid esters tripolymer, hexamethylene diisocyanate polymer.
7. a kind of novel acrylic modified rubber foam resin according to claim 1, it is characterised in that: the rubber
Particle includes styrene-isoprene-styrene block copolymer, Styrene-Butadiene-Styrene Block Copolymer, hydrogenation
Any one or more synthetic rubber in SBS, nitrile rubber.
8. a kind of preparation method of novel acrylic modified rubber foam resin, which is characterized in that comprising steps of
Dissolution dispersion under conditions of temperature is 30-60 DEG C after rubber particles and ethyl acetate, toluene are mixed sufficiently, is mixed
Close liquid；
Under conditions of temperature is 40 DEG C, monomer is added in Xiang Suoshu mixed liquor, obtains reaction solution；
Nitrogen deoxygenation 0.8-1.5H is filled with into the reaction solution；
After being warming up to 65 DEG C -85 DEG C, initiator is added；
2-3.5H is reacted under conditions of temperature is 65 DEG C -85 DEG C, increases viscosity, then proceedes to reaction 20min-40min；
Antioxidant is added, then cooling terminates reaction, obtains novel acrylic modified rubber foam resin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910724768.6A CN110396160A (en) | 2019-08-07 | 2019-08-07 | A kind of novel acrylic modified rubber foam resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910724768.6A CN110396160A (en) | 2019-08-07 | 2019-08-07 | A kind of novel acrylic modified rubber foam resin and preparation method thereof |
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ID=68327615
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300524A (en) * | 2020-11-04 | 2021-02-02 | 广东弘擎电子材料科技有限公司 | High-elasticity acrylic acid foam cotton, and preparation method and application thereof |
| CN114015227A (en) * | 2021-12-22 | 2022-02-08 | 苏州赛伍应用技术股份有限公司 | Fast-curing slow-resilience acrylic foam and preparation method and application thereof |
| CN114231201A (en) * | 2021-11-02 | 2022-03-25 | 苏州翎慧材料科技有限公司 | High-energy-absorption modified acrylic buffer material and preparation method thereof |
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| CN109836546A (en) * | 2019-03-13 | 2019-06-04 | 新纶科技（常州）有限公司 | A kind of rubber modified polymers and combinations thereof |
| CN109851724A (en) * | 2018-12-27 | 2019-06-07 | 新纶科技（常州）有限公司 | A kind of polymerization foam substrate and double faced adhesive tape and preparation method thereof |
| CN109913144A (en) * | 2019-03-13 | 2019-06-21 | 新纶科技（常州）有限公司 | A kind of preparation method of SIS elastomer graft compound A and combinations thereof and foam double-faced adhesive band |
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| CN112300524A (en) * | 2020-11-04 | 2021-02-02 | 广东弘擎电子材料科技有限公司 | High-elasticity acrylic acid foam cotton, and preparation method and application thereof |
| CN114231201A (en) * | 2021-11-02 | 2022-03-25 | 苏州翎慧材料科技有限公司 | High-energy-absorption modified acrylic buffer material and preparation method thereof |
| CN114015227A (en) * | 2021-12-22 | 2022-02-08 | 苏州赛伍应用技术股份有限公司 | Fast-curing slow-resilience acrylic foam and preparation method and application thereof |
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Application publication date: 20191101 |
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