CN102408853A - Water-based body flame-retardant acrylate adhesive and preparation method thereof - Google Patents
Water-based body flame-retardant acrylate adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN102408853A CN102408853A CN2011102231488A CN201110223148A CN102408853A CN 102408853 A CN102408853 A CN 102408853A CN 2011102231488 A CN2011102231488 A CN 2011102231488A CN 201110223148 A CN201110223148 A CN 201110223148A CN 102408853 A CN102408853 A CN 102408853A
- Authority
- CN
- China
- Prior art keywords
- monomer
- water
- flame retardant
- based body
- emulsion
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 title abstract description 12
- 239000000853 adhesive Substances 0.000 title abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract 5
- 239000000178 monomer Substances 0.000 claims abstract description 95
- 239000000839 emulsion Substances 0.000 claims abstract description 44
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000004945 emulsification Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 39
- 229920005822 acrylic binder Polymers 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 22
- -1 acrylic ester Chemical class 0.000 claims description 19
- 239000000872 buffer Substances 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 17
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 9
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000010977 jade Substances 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- KQKPFRSPSRPDEB-UHFFFAOYSA-N sumatriptan Chemical compound CNS(=O)(=O)CC1=CC=C2NC=C(CCN(C)C)C2=C1 KQKPFRSPSRPDEB-UHFFFAOYSA-N 0.000 claims description 3
- 229960000658 sumatriptan succinate Drugs 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000006172 buffering agent Substances 0.000 abstract 1
- 238000010556 emulsion polymerization method Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 239000004159 Potassium persulphate Substances 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- 235000019394 potassium persulphate Nutrition 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a water-based body flame-retardant acrylate adhesive and a preparation method thereof, belonging to the field of adhesive preparation. The adhesive is prepared by reacting a soft monomer, a hard monomer, a functional monomer, an acrylate monomer containing a flame-retardant group, an initiator, an emulsifier, a buffering agent, a molecular weight regulator, a pH regulator and deionized water. The preparation method comprises the following steps: the phosphorus-containing acrylate monomer with flame retardance and the general acrylate monomer are polymerized by adopting a pre-emulsification process and a semi-continuous emulsion polymerization method, so that the body flame-retardant copolymerization adhesive emulsion with high conversion rate and stable performance is synthesized. The invention has simple process, lower cost and excellent prepared bonding performance, and eliminates the pollution of solvent and halogen flame retardant to the environment and the influence of long-term stability brought by simple addition of inorganic or organic flame retardant.
Description
Technical field
The present invention relates to the polymer binder preparation field, a kind of water-based body flame retardant type acrylic binder and preparation method thereof is provided especially.
Background technology
Fire retardant glue on the market mostly adopts solvent type tackiness agent now, and not only raw materials cost is high, also contains some harmful chemical substances, like benzene class, ketone etc.Along with the enhancing of environmental consciousness and awareness of safety, and the progress of the Water-borne modification polymerization technique of Acrylic Acid Monomer, the aqueous binder that preparation has flame retardant resistance and stable mechanical property is necessary.And present most of flame retardant adhesive all adopts the back to add fire retardant to carry out that blend prepares; Because comprehending, the particle packing film former of water-based emulsion causes dissociating mutually of fire retardant and latex particle; Cause the inorganic or organic fire retardant of the small molecules that contains in some water soluble acrylic acid ester adhesive emulsifying agent in goods and latex to move, physicalies such as product water tolerance, bonding strength are descended to the surface, and because viscosity own is big; Mobile poor; Instability is brought a lot of inconvenience to operation, has slow, the defectives such as back the paper product easy moisture absorption, deflection deformation or the foaming of in heat pressure forming process, being heated of filming of rate of drying usually.Therefore, the aqueous binder that contains fire-retardant group in the body of preparing is that very big market outlook are arranged.
Summary of the invention
The purpose of embodiment of the present invention provides a kind of water-based body flame retardant type acrylic binder and preparation method thereof.This method has been got rid of solvent adhesiveproperties and fire-retardant equilibrium problem have been stablized, solved to pollution, the while gained composite emulsion of environment.
The objective of the invention is to realize through following technical scheme:
Embodiment of the present invention provides a kind of water-based body flame retardant type acrylic binder, and this tackiness agent is prepared from through preparatory emulsification and semi-continuous emulsion polymerizing soft monomer, hard monomer, functional monomer, the acrylic ester monomer that contains fire-retardant group, initiator, emulsifying agent, buffer reagent, molecular weight regulator, pH regulator agent and deionized water.
In the above-mentioned tackiness agent, the consumption of each raw material is by weight percentage in the said tackiness agent:
In the above-mentioned tackiness agent, said soft monomer employing carbonatoms is 4～12 propenoate.
In the above-mentioned tackiness agent, said soft monomer adopts at least a in Bing Xisuandingzhi, ethyl propenoate, the ethyl acrylate.
In the above-mentioned tackiness agent, said hard monomer adopts at least a in TEB 3K, vinyl acetate, vinylbenzene, vinyl cyanide, the vinyl acetate.
In the above-mentioned tackiness agent, said function monomer adopts at least a in Hydroxyethyl acrylate, vinylformic acid, methylacrylic acid, N hydroxymethyl acrylamide and the Phthalic acid, diallyl ester.
In the above-mentioned tackiness agent, the said acrylic ester monomer that contains fire-retardant group is the acrylic type phosphorous-containing monomers.
In the above-mentioned tackiness agent, said initiator adopts persulphate;
Said emulsifying agent adopts at least a in phenolic ether sulphate, the semi-annular jade pendant base SUMATRIPTAN SUCCINATE.
Said buffer reagent adopts at least a in bicarbonate of ammonia, the sodium hydrogencarbonate;
Said molecular weight regulator adopts n-dodecyl mercaptan;
Ammoniacal liquor is adopted in said pH regulator agent.
Embodiment of the present invention also provides a kind of preparation method of water-based body flame retardant type acrylic binder, may further comprise the steps:
Get each raw material of preparation tackiness agent by above-mentioned each prescription;
In the polymeric kettle under the whipped state, add the deionized water that accounts for whole deionized water gross weights 40～50% and account for the emulsifying agent of whole emulsifying agent gross weights 10%～20%, and add whole buffer reagents, wait to stir;
In preparatory emulsification still; Add the deionized water and the remaining emulsifying agent that account for whole deionized water gross weights 30%～40%; Under 500～1000 rev/mins stirring velocity, stir fast and make it dissolving; Drip then by soft monomer, hard monomer, function monomer and the acrylic ester monomer that contains fire-retardant group and mix the mixed solution forms, after dropwising, low whipping speed is that 220～300 rev/mins state continues stirring 1～2 hour down;, the pH value of regulating reaction system in the preparatory emulsification still obtains pre-emulsion for slightly acidic or neutrality;
In above-mentioned polymeric kettle, add the pre-emulsion that accounts for the above-mentioned whole pre-emulsion gross weights 10%～30% that make; After stirring and being warming up to 86 ± 1 ℃, add molecular weight regulator that accounts for whole molecular weight regulator gross weights 40%～80% and the initiator that accounts for whole initiator gross weights 10%～30%; After treating that emulsion in the said polymeric kettle occurs reacting 10～30 minutes again behind the blue light; In said polymeric kettle, drip remaining pre-emulsion and remaining initiator; Rate of addition is controlled at the still wall not to be had obvious backflow and can dropwise at 4～5 hours; Temperature of reaction is controlled at 86 ± 1 ℃, and stirring velocity is 220～300 rev/mins; After 1～2h is carried out in dropping, remaining molecular weight regulator is joined in the said polymeric kettle;
After waiting to drip end, make said polymeric kettle continue insulation reaction 30 minutes～1.5 hours, be cooled to then below 40 ℃, the pH value of regulating emulsion in the said polymeric kettle is 7, filters discharging, promptly obtains water-based body flame retardant type acrylic binder.
Can find out by the above-mentioned technical scheme that provides; Through being raw material, be prepared into a kind of water-based body flame retardant type acrylic binder in the embodiment of the present invention through preparatory emulsification and semi-continuous emulsion polymerizing with soft monomer, hard monomer, functional monomer, the acrylic ester monomer that contains fire-retardant group, initiator, emulsifying agent, buffer reagent, molecular weight regulator, pH regulator agent and deionized water.This tackiness agent adhesiveproperties is good, and preparation technology is simple, and good stability can be avoided the pollution to environment of solvent, halogenated flame retardant, and avoids through the simple outer bad influence of tackiness agent permanent stability inorganic or that organic fire-resisting brings of adding.
Embodiment
Below in conjunction with specific embodiment the technical scheme among the present invention is carried out clear, intactly description, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on embodiments of the invention, those of ordinary skills belong to protection scope of the present invention not making the every other embodiment that is obtained under the creative work prerequisite.
Do to describe in detail further in the face of the embodiment of the invention down.
The embodiment of the invention provides a kind of water-based body flame retardant type acrylic binder, and this tackiness agent is prepared from through preparatory emulsification and semi-continuous emulsion polymerizing soft monomer, hard monomer, functional monomer, the acrylic ester monomer that contains fire-retardant group, initiator, emulsifying agent, buffer reagent, molecular weight regulator, pH regulator agent and deionized water.
The consumption of each raw material is by weight percentage in the above-mentioned tackiness agent: soft monomer 30～45%, hard monomer 0.7%～5%, function monomer 1%～5%, the acrylic ester monomer 5%～15% that contains fire-retardant group, initiator 0.4%～2.0%, emulsifying agent 0.8～3.0%, buffer reagent 1.0%～3.0%, molecular weight regulator 0.1%～1.0%.PH regulator agent 1%～5%, deionized water 45%～60%.
It is 4～12 propenoate that soft monomer in the above-mentioned tackiness agent adopts carbonatoms, specifically can adopt at least a in Bing Xisuandingzhi, ethyl propenoate, the ethyl acrylate.This soft monomer can form the polymkeric substance that second-order transition temperature is low, have fine tack.
Hard monomer in the above-mentioned tackiness agent adopts at least a in TEB 3K, vinyl acetate, vinylbenzene, vinyl cyanide, the vinyl acetate.This hard monomer mainly plays cohesive action, can produce the multipolymer with better cohesive strength and higher use temperature with the soft monomer copolymerization, in multipolymer (being tackiness agent), plays skeleton function.
Function monomer in the above-mentioned tackiness agent adopts at least a in Hydroxyethyl acrylate, vinylformic acid, methylacrylic acid, N hydroxymethyl acrylamide and the Phthalic acid, diallyl ester.This function monomer can be given the adhesive reaction characteristic through the active function groups of himself, in order to characteristics such as adhesiveproperties and the water tolerance of improvement tackiness agent, weathering resistance, solvent resistances.
The acrylic ester monomer that contains fire-retardant group in the above-mentioned tackiness agent is the acrylic type phosphorous-containing monomers.This acrylic ester monomer that contains fire-retardant group plays an important role to effective flame retardant resistance of improving tackiness agent.
Initiator in the above-mentioned tackiness agent adopts persulphate;
Emulsifying agent in the above-mentioned tackiness agent adopts at least a in phenolic ether sulphate, the semi-annular jade pendant base SUMATRIPTAN SUCCINATE.
Buffer reagent in the above-mentioned tackiness agent adopts at least a in bicarbonate of ammonia, the sodium hydrogencarbonate;
Molecular weight regulator in the above-mentioned tackiness agent adopts n-dodecyl mercaptan;
Ammoniacal liquor is adopted in pH regulator agent in the above-mentioned tackiness agent.
The preparation method of above-mentioned water-based body flame retardant type acrylic binder specifically may further comprise the steps:
Get each raw material of preparation tackiness agent by above-mentioned prescription;
In the polymeric kettle under the whipped state, add the deionized water that accounts for whole deionized water gross weights 40～50% and account for the emulsifying agent of whole emulsifying agent gross weights 10%～20%, and add whole buffer reagents, wait to stir;
In preparatory emulsification still; Add the deionized water and the remaining emulsifying agent that account for whole deionized water gross weights 30%～40%; Under 500～1000 rev/mins stirring velocity, stir fast and make it dissolving; Drip then by soft monomer, hard monomer, function monomer and the acrylic ester monomer that contains fire-retardant group and mix the mixed solution forms, after dropwising, low whipping speed is that 220～300 rev/mins state continues stirring 1～2 hour down;, the pH value of regulating reaction system in the preparatory emulsification still obtains pre-emulsion for slightly acidic or neutrality;
In above-mentioned polymeric kettle, add the pre-emulsion that accounts for the above-mentioned whole pre-emulsion gross weights 10%～30% that make; After stirring and being warming up to 86 ± 1 ℃, add molecular weight regulator that accounts for whole molecular weight regulator gross weights 40%～80% and the initiator that accounts for whole initiator gross weights 10%～30%; After treating that emulsion in the said polymeric kettle occurs reacting 10～30 minutes again behind the blue light; In said polymeric kettle, drip remaining pre-emulsion and remaining initiator; Rate of addition is controlled at the still wall not to be had obvious backflow and can dropwise at 4～5 hours; Temperature of reaction is controlled at 86 ± 1 ℃, and stirring velocity is 220～300 rev/mins; After 1～2h is carried out in dropping, remaining molecular weight regulator is joined in the said polymeric kettle;
After waiting to drip end, make said polymeric kettle continue insulation reaction 30 minutes～1.5 hours, be cooled to then below 40 ℃, the pH value of regulating emulsion in the said polymeric kettle is 7, filters discharging, promptly obtains water-based body flame retardant type acrylic binder.
Through specific embodiment the present invention is described further below.
Embodiment 1
Present embodiment provides a kind of water-based body flame retardant type acrylic binder, and the preparation of this tackiness agent is filled a prescription as follows:
Bing Xisuandingzhi (soft monomer) 40 weight parts; TEB 3K (hard monomer) 3 weight parts, Hydroxyethyl acrylate and vinylformic acid (function monomer) 2 weight parts, acrylic type phosphorous-containing monomers (acrylic ester monomer that contains fire-retardant group) 5 weight parts; Ammonium persulphate (initiator) 0.8 weight part; OP-10 (emulsifying agent) 0.8 weight part, sodium hydrogencarbonate (buffer reagent) 1.0 weight parts, n-dodecyl mercaptan (molecular weight regulator) 0.6 weight part; Ammoniacal liquor (pH regulator agent) 1.0 weight parts, deionized water 45.8 amount parts.
Above-mentioned water-based body flame retardant type acrylic binder is prepared from through preparatory emulsification and semi-continuous emulsion polymerizing, specifically may further comprise the steps:
(a) in the polymeric kettle of continuous stirring, add 10 parts by weight of deionized water prepare and the OP-10 (emulsifying agent) of 0.16 weight part, and add the sodium hydrogencarbonate (buffer reagent) of 1.0 weight parts, wait to stir;
(b) in preparatory emulsification still; Take by weighing the deionized water of 40 weight parts and the OP-10 (emulsifying agent) of 0.64 weight part; Stir (under 500～1000 rev/mins stirring velocity) fast and make it dissolving; Mixed solution 50 weight parts of dropwise addition of acrylic acid butyl ester (soft monomer), TEB 3K (hard monomer), Hydroxyethyl acrylate, vinylformic acid (function monomer) and acrylic type phosphorous-containing monomers (acrylic ester monomer that contains fire-retardant group) then; After dropwising, continue to stir 1 hour, the pH value of conditioned reaction system is that 6.5 promptly to obtain pre-emulsion subsequent use;
(c) it is rebasing in the polymeric kettle of step a, to add the pre-emulsion of 9 weight parts, stir and be warming up to 86 ± 1 ℃ after, add the n-dodecyl mercaptan (molecular weight regulator) of 0.24 weight part and the Sodium Persulfate (initiator) of the rebasing usefulness of 0.06 weight part fast;
(d) treat that emulsion occurs reacting for some time (30min) again behind the blue light in the above-mentioned polymeric kettle after; Begin in step c polymeric kettle, to drip remaining pre-emulsion and remaining Sodium Persulfate (initiator); The still wall that rate of addition is controlled at polymeric kettle does not have obvious backflow and can dropwise at certain hour (4.5h) is advisable; Temperature of reaction should be controlled at 86 ± 1 ℃, and stirring velocity is roughly at 220～300r/min;
(e) after remaining pre-emulsion of dropping and remaining initiator carry out 2.5h in polymeric kettle, remaining molecular weight regulator lauryl mercaptan is joined in the polymeric kettle;
(f) wait drip to finish after, continue insulation reaction 1h, be cooled to then below 40 ℃, the pH value of regulating emulsion is 7, the filtration discharging, the white emulsion that obtains fine and smooth blueing light is water-based body flame retardant type acrylic binder.
Embodiment 2
Present embodiment provides a kind of water-based body flame retardant type acrylic binder, and the preparation of this tackiness agent is filled a prescription as follows:
Bing Xisuandingzhi (soft monomer) 35 weight parts, vinyl acetate (hard monomer) 3 weight parts, Hydroxyethyl acrylate and vinylformic acid (function monomer) 2 weight parts; Acrylic type phosphorous-containing monomers (acrylic ester monomer that contains fire-retardant group) 10 weight parts, Potassium Persulphate (initiator) 0.6 weight part, CO436 (emulsifying agent) 0.8 weight part; Sodium hydrogencarbonate (buffer reagent) 1.0 weight parts; N-dodecyl mercaptan (molecular weight regulator) 0.6 weight part, ammoniacal liquor (pH regulator agent) 0.2 weight part, deionized water 46 amount parts;
Above-mentioned water-based body flame retardant type acrylic binder is prepared from through preparatory emulsification and semi-continuous emulsion polymerizing, specifically may further comprise the steps:
(a) in the polymeric kettle that constantly stirs, add the deionized water of 10 weight parts that prepare and the CO436 (emulsifying agent) of 0.16 weight part, and add 1.0 weight part sodium hydrogencarbonates (buffer reagent), wait to stir;
(b) in preparatory emulsification still; Take by weighing the deionized water of 40 weight parts and the CO436 (emulsifying agent) of 0.64 weight part; Stir (under 500～1000 rev/mins stirring velocity) fast and make it dissolving; Mixed solution 50 weight parts of dropwise addition of acrylic acid butyl ester (soft monomer), vinyl acetate (hard monomer), Hydroxyethyl acrylate, vinylformic acid (function monomer) and acrylic type phosphorous-containing monomers (acrylic ester monomer that contains fire-retardant group) then; After dropwising, continue to stir 1 hour, regulating pH is that slightly acidic or neutrality (the pH value is 6～7) back are subsequent use;
(c) it is rebasing in step a polymeric kettle, to add the pre-emulsion of 9 weight parts, stir and be warming up to 86 ± 1 ℃ after, add the lauryl mercaptan (molecular weight regulator) of 0.24 weight part and the Potassium Persulphate (initiator) of the rebasing usefulness of 0.06 weight part fast;
(d) treat that (1 hour) appears reacting for some time behind the blue light in emulsion again after; Begin in step c polymeric kettle, to drip remaining pre-emulsion and remaining Potassium Persulphate (initiator); The still wall that rate of addition is controlled at polymeric kettle does not have obvious backflow and can dropwise at certain hour (5h) is advisable; Temperature of reaction should be controlled at 86 ± 1 ℃, and stirring velocity is roughly at 220～300r/min;
(e) after 2h is carried out in dropping, remaining lauryl mercaptan (molecular weight regulator) is joined in the polymeric kettle;
(f) wait drip to finish after, continue insulation reaction 1h, be cooled to then below 40 ℃, regulating pH is 7, filters discharging, the white emulsion that obtains fine and smooth blueing light is water-based body flame retardant type acrylic binder.
Embodiment 3
Present embodiment provides a kind of water-based body flame retardant type acrylic binder, and the preparation of this tackiness agent is filled a prescription as follows:
Bing Xisuandingzhi (soft monomer) 30 weight parts, vinyl acetate (hard monomer) 1 weight part, Hydroxyethyl acrylate and vinylformic acid (function monomer) 1 weight part; Acrylic type phosphorous-containing monomers (acrylic ester monomer that contains fire-retardant group) 5 weight parts, Potassium Persulphate (initiator) 0.6 weight part, CO436 (emulsifying agent) 0.8 weight part; Sodium hydrogencarbonate (buffer reagent) 1.0 weight parts; N-dodecyl mercaptan (molecular weight regulator) 0.6 weight part, ammoniacal liquor (pH regulator agent) 1.0 weight parts, deionized water 59 weight parts;
Above-mentioned water-based body flame retardant type acrylic binder is prepared from through preparatory emulsification and semi-continuous emulsion polymerizing, specifically may further comprise the steps:
(a) in the polymeric kettle that constantly stirs, add 10 parts by weight of deionized water and the 0.16 weight part CO436 (emulsifying agent) for preparing, and add sodium hydrogencarbonate (buffer reagent) 1.0 weight parts, wait to stir;
(b) in preparatory emulsification still; Take by weighing the deionized water of 40 weight parts and the CO436 (emulsifying agent) of 0.64 weight part; Stir (under 500～1000 rev/mins stirring velocity) fast and make it dissolving; Mixed solution 50 weight parts of dropwise addition of acrylic acid butyl ester (soft monomer), vinyl acetate (hard monomer), Hydroxyethyl acrylate, vinylformic acid (function monomer) and acrylic type phosphorous-containing monomers (acrylic ester monomer that contains fire-retardant group) then; After dropwising, continue to stir 1 hour, regulating pH is that slightly acidic or neutrality (the pH value is 6～7) back are subsequent use;
(c) it is rebasing in step a polymeric kettle, to add the pre-emulsion of 9 weight parts, stir and be warming up to 86 ± 1 ℃ after, add the lauryl mercaptan (molecular weight regulator) of 0.24 weight part and the Potassium Persulphate (initiator) of the rebasing usefulness of 0.06 weight part fast;
(d) treat that (1 hour) appears reacting for some time behind the blue light in emulsion again after; Begin in step c polymeric kettle, to drip remaining pre-emulsion and remaining Potassium Persulphate (initiator); The still wall that rate of addition is controlled at polymeric kettle does not have obvious backflow and can dropwise at certain hour (5h) is advisable; Temperature of reaction should be controlled at 86 ± 1 ℃, and stirring velocity is roughly at 220～300r/min;
(e) after 2h is carried out in dropping, remaining lauryl mercaptan (molecular weight regulator) is joined in the polymeric kettle;
(f) wait drip to finish after, continue insulation reaction 1h, be cooled to then below 40 ℃, regulating pH is 7, filters discharging, the white emulsion that obtains fine and smooth blueing light is water-based body flame retardant type acrylic binder.
Water-based body flame retardant type acrylic binder in the embodiment of the invention is a raw material with soft monomer, hard monomer, functional monomer, the acrylic ester monomer that contains fire-retardant group, initiator, emulsifying agent, buffer reagent, molecular weight regulator, pH regulator agent and deionized water, through preparatory emulsification and semi-continuous emulsion polymerizing preparation and.This tackiness agent adhesiveproperties is good, and preparation technology is simple, and good stability can be avoided the pollution to environment of solvent, halogenated flame retardant, and avoids through the simple outer bad influence of tackiness agent permanent stability inorganic or that organic fire-resisting brings of adding.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technician who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (9)
1. water-based body flame retardant type acrylic binder; It is characterized in that this tackiness agent is prepared from through preparatory emulsification and semi-continuous emulsion polymerizing soft monomer, hard monomer, functional monomer, the acrylic ester monomer that contains fire-retardant group, initiator, emulsifying agent, buffer reagent, molecular weight regulator, pH regulator agent and deionized water.
2. water-based body flame retardant type acrylic binder as claimed in claim 1 is characterized in that the consumption of each raw material is by weight percentage in the said tackiness agent:
3. according to claim 1 or claim 2 water-based body flame retardant type acrylic binder is characterized in that, it is 4～12 propenoate that said soft monomer adopts carbonatoms.
4. according to claim 1 or claim 2 water-based body flame retardant type acrylic binder is characterized in that, said soft monomer adopts at least a in Bing Xisuandingzhi, ethyl propenoate, the ethyl acrylate.
5. according to claim 1 or claim 2 water-based body flame retardant type acrylic binder is characterized in that, said hard monomer adopts at least a in TEB 3K, vinyl acetate, vinylbenzene, vinyl cyanide, the vinyl acetate.
6. according to claim 1 or claim 2 water-based body flame retardant type acrylic binder; It is characterized in that said function monomer adopts at least a in Hydroxyethyl acrylate, vinylformic acid, methylacrylic acid, N hydroxymethyl acrylamide and the Phthalic acid, diallyl ester.
7. according to claim 1 or claim 2 water-based body flame retardant type acrylic binder is characterized in that the said acrylic ester monomer that contains fire-retardant group is the acrylic type phosphorous-containing monomers.
8. according to claim 1 or claim 2 water-based body flame retardant type acrylic binder is characterized in that, said initiator adopts persulphate;
Said emulsifying agent adopts at least a in phenolic ether sulphate, the semi-annular jade pendant base SUMATRIPTAN SUCCINATE.
Said buffer reagent adopts at least a in bicarbonate of ammonia, the sodium hydrogencarbonate;
Said molecular weight regulator adopts n-dodecyl mercaptan;
Ammoniacal liquor is adopted in said pH regulator agent.
9. the preparation method of a water-based body flame retardant type acrylic binder is characterized in that, may further comprise the steps:
Get each raw material of preparation tackiness agent by each prescription of aforesaid right requirement 1～8;
In the polymeric kettle under the whipped state, add the deionized water that accounts for whole deionized water gross weights 40～50% and account for the emulsifying agent of whole emulsifying agent gross weights 10%～20%, and add whole buffer reagents, wait to stir;
In preparatory emulsification still; Add the deionized water and the remaining emulsifying agent that account for whole deionized water gross weights 30%～40%; Under 500～1000 rev/mins stirring velocity, stir fast and make it dissolving; Drip then by soft monomer, hard monomer, function monomer and the acrylic ester monomer that contains fire-retardant group and mix the mixed solution form; After dropwising, low whipping speed is that 220～300 rev/mins state continues down to stir 1～2 hour, and the pH value of regulating reaction system in the preparatory emulsification still obtains pre-emulsion for slightly acidic or neutrality;
In above-mentioned polymeric kettle, add the pre-emulsion that accounts for the above-mentioned whole pre-emulsion gross weights 10%～30% that make; After stirring and being warming up to 86 ± 1 ℃, add molecular weight regulator that accounts for whole molecular weight regulator gross weights 40%～80% and the initiator that accounts for whole initiator gross weights 10%～30%; After treating that emulsion in the said polymeric kettle occurs reacting 10～30 minutes again behind the blue light; In said polymeric kettle, drip remaining pre-emulsion and remaining initiator; Rate of addition is controlled at the still wall not to be had obvious backflow and can dropwise at 4～5 hours; Temperature of reaction is controlled at 86 ± 1 ℃, and stirring velocity is 220～300 rev/mins; After 1～2h is carried out in dropping, remaining molecular weight regulator is joined in the said polymeric kettle;
After waiting to drip end, make said polymeric kettle continue insulation reaction 30 minutes～1.5 hours, be cooled to then below 40 ℃, the pH value of regulating emulsion in the said polymeric kettle is 7, filters discharging, promptly obtains water-based body flame retardant type acrylic binder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110223148.8A CN102408853B (en) | 2011-08-04 | 2011-08-04 | Water-based body flame-resistant acrylate adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110223148.8A CN102408853B (en) | 2011-08-04 | 2011-08-04 | Water-based body flame-resistant acrylate adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102408853A true CN102408853A (en) | 2012-04-11 |
| CN102408853B CN102408853B (en) | 2014-07-02 |
Family
ID=45911210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110223148.8A Expired - Fee Related CN102408853B (en) | 2011-08-04 | 2011-08-04 | Water-based body flame-resistant acrylate adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408853B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703002A (en) * | 2012-06-26 | 2012-10-03 | 上海中新裕祥化工有限公司 | Environment-friendly high temperature-resistant and easily-stripped pressure-sensitive adhesive for electronic industry and preparation method thereof |
| CN103865443A (en) * | 2012-12-07 | 2014-06-18 | 上海华谊丙烯酸有限公司 | Transfer-type adhesive and its preparation method |
| CN105085790A (en) * | 2015-09-10 | 2015-11-25 | 湖南工学院 | Ingrain fireproofing type acrylate emulsion as well as preparation method and application thereof |
| CN105754522A (en) * | 2014-12-16 | 2016-07-13 | 浙江新力化工有限公司 | Flame retardant adhesive for glass fiber grid positioning and preparation method thereof |
| CN107573799A (en) * | 2017-09-22 | 2018-01-12 | 陈晨特 | A kind of phosphorus nitrogen cooperates with self-flame-retardant environment friendly wood coatings |
| CN108192512A (en) * | 2018-01-03 | 2018-06-22 | 东莞市山森防火材料有限公司 | A kind of novel environment friendly fire-proof belt and its preparation |
| CN109266257A (en) * | 2018-09-29 | 2019-01-25 | 广州都邦材料科技有限公司 | Acrylic Pressure Sensitive Adhesive and preparation method thereof, electronic product |
| CN110407979A (en) * | 2019-08-09 | 2019-11-05 | 苏州高泰电子技术股份有限公司 | Pressure-sensitive gum resin and light transmission flame-retardant double sided tape comprising it |
| CN110628258A (en) * | 2019-09-17 | 2019-12-31 | 中国石油大学(华东) | A water-based phosphorus-containing ultra-thin fireproof coating material and its preparation method |
| CN111303817A (en) * | 2020-02-19 | 2020-06-19 | 北京高盟新材料股份有限公司 | Flame-retardant waterborne polyurethane adhesive and preparation method thereof |
| CN113880981A (en) * | 2021-08-11 | 2022-01-04 | 南通大学 | Phosphorus-containing polyacrylate adhesive and preparation method and application thereof |
| CN114196150A (en) * | 2021-12-14 | 2022-03-18 | 杭州弘毅智创科技有限公司 | Preparation method and device of phosphorus-containing intrinsic flame-retardant polyacrylate composite material |
| CN114231219A (en) * | 2021-12-29 | 2022-03-25 | 山东灵晓新材料有限公司 | Water-based acrylic acid adhesive and preparation method thereof |
| CN115322706A (en) * | 2022-08-31 | 2022-11-11 | 福建华峰新材料有限公司 | Elastic and smooth adhesive and preparation method thereof |
| CN115746754A (en) * | 2022-11-02 | 2023-03-07 | 广东银洋环保新材料有限公司 | Water-based environment-friendly flame-retardant adhesive as well as preparation method and application thereof |
| CN116239976A (en) * | 2022-12-23 | 2023-06-09 | 河北省地质环境监测院 | Core specimen shaping glue and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805567A (en) * | 2010-03-12 | 2010-08-18 | 北京化工大学 | Preparation method of combined phosphorus type flame-retardant acrylate pressure-sensitive adhesive |
-
2011
- 2011-08-04 CN CN201110223148.8A patent/CN102408853B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805567A (en) * | 2010-03-12 | 2010-08-18 | 北京化工大学 | Preparation method of combined phosphorus type flame-retardant acrylate pressure-sensitive adhesive |
Non-Patent Citations (2)
| Title |
|---|
| 吴芮: "阻燃型丙烯酸系压敏粘合剂的制备与性能", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 夏宇正等: "结合磷型阻燃丙烯酸酯共聚物乳液的合成与性能", 《涂料工业》 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703002A (en) * | 2012-06-26 | 2012-10-03 | 上海中新裕祥化工有限公司 | Environment-friendly high temperature-resistant and easily-stripped pressure-sensitive adhesive for electronic industry and preparation method thereof |
| CN103865443A (en) * | 2012-12-07 | 2014-06-18 | 上海华谊丙烯酸有限公司 | Transfer-type adhesive and its preparation method |
| CN103865443B (en) * | 2012-12-07 | 2016-08-24 | 上海华谊丙烯酸有限公司 | Transfevent binding agent and preparation method thereof |
| CN105754522A (en) * | 2014-12-16 | 2016-07-13 | 浙江新力化工有限公司 | Flame retardant adhesive for glass fiber grid positioning and preparation method thereof |
| CN105754522B (en) * | 2014-12-16 | 2018-08-21 | 浙江科力森化学有限公司 | Fire retardant glue and preparation method thereof for fiberglass gridding positioning |
| CN105085790A (en) * | 2015-09-10 | 2015-11-25 | 湖南工学院 | Ingrain fireproofing type acrylate emulsion as well as preparation method and application thereof |
| CN107573799A (en) * | 2017-09-22 | 2018-01-12 | 陈晨特 | A kind of phosphorus nitrogen cooperates with self-flame-retardant environment friendly wood coatings |
| CN108192512B (en) * | 2018-01-03 | 2020-11-06 | 东莞市山森实业有限公司 | Environment-friendly fireproof adhesive tape and preparation thereof |
| CN108192512A (en) * | 2018-01-03 | 2018-06-22 | 东莞市山森防火材料有限公司 | A kind of novel environment friendly fire-proof belt and its preparation |
| CN109266257A (en) * | 2018-09-29 | 2019-01-25 | 广州都邦材料科技有限公司 | Acrylic Pressure Sensitive Adhesive and preparation method thereof, electronic product |
| CN109266257B (en) * | 2018-09-29 | 2021-04-06 | 广州都邦新材料科技股份有限公司 | Acrylate pressure-sensitive adhesive, preparation method thereof and electronic product |
| CN110407979A (en) * | 2019-08-09 | 2019-11-05 | 苏州高泰电子技术股份有限公司 | Pressure-sensitive gum resin and light transmission flame-retardant double sided tape comprising it |
| CN110628258A (en) * | 2019-09-17 | 2019-12-31 | 中国石油大学(华东) | A water-based phosphorus-containing ultra-thin fireproof coating material and its preparation method |
| CN111303817A (en) * | 2020-02-19 | 2020-06-19 | 北京高盟新材料股份有限公司 | Flame-retardant waterborne polyurethane adhesive and preparation method thereof |
| CN113880981A (en) * | 2021-08-11 | 2022-01-04 | 南通大学 | Phosphorus-containing polyacrylate adhesive and preparation method and application thereof |
| CN114196150A (en) * | 2021-12-14 | 2022-03-18 | 杭州弘毅智创科技有限公司 | Preparation method and device of phosphorus-containing intrinsic flame-retardant polyacrylate composite material |
| CN114231219A (en) * | 2021-12-29 | 2022-03-25 | 山东灵晓新材料有限公司 | Water-based acrylic acid adhesive and preparation method thereof |
| CN115322706A (en) * | 2022-08-31 | 2022-11-11 | 福建华峰新材料有限公司 | Elastic and smooth adhesive and preparation method thereof |
| CN115322706B (en) * | 2022-08-31 | 2023-08-15 | 福建华峰新材料有限公司 | Elastic sliding adhesive and preparation method thereof |
| CN115746754A (en) * | 2022-11-02 | 2023-03-07 | 广东银洋环保新材料有限公司 | Water-based environment-friendly flame-retardant adhesive as well as preparation method and application thereof |
| CN116239976A (en) * | 2022-12-23 | 2023-06-09 | 河北省地质环境监测院 | Core specimen shaping glue and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102408853B (en) | 2014-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102408853A (en) | Water-based body flame-retardant acrylate adhesive and preparation method thereof | |
| CN101921373B (en) | Acrylic modified epoxy resin emulsion and preparation method thereof | |
| CN105131866B (en) | A kind of iron sheet panel composite surface aqueous adhesive and preparation method thereof | |
| CN102533186B (en) | Adhesive for alkali resistant acrylate glass fiber mesh cloth shaping, and preparation method thereof | |
| CN102408513B (en) | Preparation method of phosphate modified acrylate emulsion | |
| CN109824818A (en) | A kind of multi-crosslinking modified core-shell structure room temperature self-crosslinking acrylic emulsion and preparation method thereof | |
| CN102718930A (en) | Organic silicon modified acrylate emulsion and preparation method thereof | |
| CN103131354B (en) | Styrene modified polyvinyl acetate emulsion and preparation method | |
| CN102533177A (en) | High water resistance emulsion polyacrylate pressure-sensitive adhesive and preparation method and application thereof | |
| CN102391800B (en) | Water-based flame-retardant acrylate pressure sensitive adhesive and preparation method thereof | |
| CN102993355A (en) | Preparation method of acrylate microemulsion with high solid content | |
| CN102633931A (en) | Styrene-acrylic emulsion and preparation method and application thereof | |
| CN103087255B (en) | Crosslinking fluorine modified acrylic ester nanometer polymer emulsion and preparation method thereof | |
| CN102603998A (en) | Preparation method of high solid content epoxy modified acrylic resin emulsion | |
| CN101864025A (en) | Preparation method and application of polyacrylate microgel emulsion | |
| CN105367697A (en) | Silicone acrylic emulsion having core-shell structure and preparation method thereof | |
| CN102838939A (en) | Modified water-base nano binder | |
| CN102070741B (en) | Heat-sealing adhesive emulsion and preparation method thereof | |
| CN106832080A (en) | A kind of woodcare paint styrene-acrylate core/shell emulsion and preparation method thereof | |
| CN109651558B (en) | Self-crosslinking core-shell structure water-based acrylic acid dispersion and preparation method and application thereof | |
| CN103059183A (en) | Flame retardant polymethyl methacrylate and preparation method thereof | |
| CN101531736A (en) | Synthetic styrene-acrylic latex | |
| CN109369839A (en) | A kind of self-cross linking type vinyl chloride copolymer lotion and preparation method thereof | |
| CN106065044A (en) | A kind of preparation method of woodcare paint styrene-acrylic emulsion | |
| CN103304727B (en) | A kind of hud typed elastic emulsion, coating and preparation method thereof containing this kind of emulsion |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140702 Termination date: 20210804 |