CN102532371B - Preparation method of film-forming agent for glass fiber injection yarn - Google Patents
Preparation method of film-forming agent for glass fiber injection yarn Download PDFInfo
- Publication number
- CN102532371B CN102532371B CN 201210016030 CN201210016030A CN102532371B CN 102532371 B CN102532371 B CN 102532371B CN 201210016030 CN201210016030 CN 201210016030 CN 201210016030 A CN201210016030 A CN 201210016030A CN 102532371 B CN102532371 B CN 102532371B
- Authority
- CN
- China
- Prior art keywords
- agent
- preparation
- film
- forming agent
- glass fiber
- 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.)
- Active
Links
Abstract
The invention discloses a preparation method of a film-forming agent for a glass fiber injection yarn. The preparation method comprises the following steps of: mixing a protective colloid, an emulsifying agent and a pH buffering agent with water to obtain a first mixed solution; and adding an oxidizing agent and a reducing agent into the first mixed solution, dropping a vinyl acetate monomer, andperforming polymerization reaction to obtain the film-forming agent for the glass fiber injection yarn. Compared with the prior art, the preparation method disclosed by the invention has the characteristic that an oxidation-reduction system is used for initiating the polymerization of a free-radical emulsion, namely, an oxidation-reduction reaction happens between the oxidizing agent and the reducing agent to generate energy so as to initiate free radicals of the polymerization. Because the oxidation-reduction system greatly reduces activation energy for generating the free radicals, and the productivity is improved by increasing the reaction rate of the polymerization, so that the molecular weight of the film-forming agent is increased. Experimental results show that the molecular weightof a polyvinyl acetate emulsion prepared by the preparation method disclosed by the invention is between 30,000 and 80,000, and the glass fiber of the film-forming agent, prepared by the preparation method, has high stiffness and cutting performance.
Description
Technical field
The present invention relates to glass-fibre technology for making field, more particularly, relate to a kind of preparation method of film-forming agent for glass fiber injection yarn.
Background technology
Glass fiber infiltration agent is a kind of surface treatment agent that applies for fiberglass surfacing, and is most important to the manufacturing of glass fibre, determined transaction capabilities and the performance of fiber in matrix material of fiber.Treating compound is to be mixed by membrane-forming agent, coupling agent and static inhibitor etc. to form the polycomponent aqueous solution or emulsion, and energy effectively lubricating fiberglass surfacing makes glass fibre smooth, soft, wear-resisting, and gives the performance of later stage matrix material brilliance.The effect for the treatment of compound is mainly manifested in the following aspects: lubrication protection effect, bonding boundling effect, prevent the accumulation of fiberglass surfacing static charge and make glass fibre obtain with the good consistency of base material etc.Under the effect for the treatment of compound, fiberglass product has the application performances such as desirable physicals, mechanical property, chemical property, electric property and ageing-resistant performance.
Membrane-forming agent is most important component in the glass fiber treating compound, can form a kind of film with continuous uniform of the performances such as certain flexibility, extensibility and rub resistance on the glass surface, and the use properties that reaches the glass later stage is had extremely important effect.The membrane-forming agent that uses in spraying yarn at present mainly is divided into four large classes, comprises epoxies membrane-forming agent, polyester membrane-forming agent, polyurethanes membrane-forming agent and polyvinyl acetate membrane-forming agent.Wherein, epoxy resin film-forming agent is mainly the small molecular weight epoxy resin film-forming agent, and high molecular expoxy resin is solid at normal temperatures, fusing point is higher, the emulsification difficulty, and the organic solvent addition is larger, very harsh to emulsification condition and equipment requirements, thus limited its use; The synthesis technique of polyester membrane-forming agent is complicated, needs pyroreaction and production cycle long, and cost is higher, has limited the popularization of polyester membrane-forming agent; The expensive raw material price of polyurethanes membrane-forming agent, high cost, range of application is also narrow.Compare with above-mentioned membrane-forming agent, the polyvinyl acetate membrane-forming agent is widely applied in spraying yarn production owing to have the characteristics such as simple, the cheap and static of technique is few.
Prior art has been carried out widely report to polyvinyl acetate membrane-forming agent and preparation method thereof; wherein; main implementation is: take vinyl acetate or with other monomers as monomer; under protective colloid action, come initiation reaction by the thermolysis system, obtain aqueous polyvinyl acetate emulsion by 4～5 hours polyreactions.But the molecular weight of the aqueous polyvinyl acetate emulsion of aforesaid method preparation is lower, be difficult for giving the good stiffness of precursor and cutting property, and price is higher.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of film-forming agent for glass fiber injection yarn, the membrane-forming agent molecular weight of the method preparation is larger, uses the glass fibre of the membrane-forming agent of the method preparation to have good stiffness and cutting property.
In order to solve above technical problem, the invention provides a kind of preparation method of film-forming agent for glass fiber injection yarn, may further comprise the steps:
Step a) is mixed protective colloid, emulsifying agent, pH buffer reagent and water, obtains the first mixing solutions;
Step b) in described the first mixing solutions, adds Oxidizing and Reducing Agents, drip Vinyl Acetate Monomer, obtain film-forming agent for glass fiber injection yarn after the polyreaction, described reductive agent is iron protochloride, mercaptan, S-WAT or ferrous sulfate, and described oxygenant is hydrogen peroxide, t-butyl hydroperoxide, isopropyl benzene hydroperoxide or Sodium Persulfate.
Preferably, described step b) be specially: step b1) in described the first mixing solutions, add oxygenant; Step b2) to described step b1) drip Vinyl Acetate Monomer in the product that obtains, add reductive agent in batches, obtain film-forming agent for glass fiber injection yarn after the polyreaction, described reductive agent is iron protochloride, mercaptan, S-WAT or ferrous sulfate, and described oxygenant is hydrogen peroxide, t-butyl hydroperoxide, isopropyl benzene hydroperoxide or Sodium Persulfate.
The temperature of polyreaction preferably, described step b2) is 65～85 ℃.
Preferably, reductive agent adds the dropping mode that adopts described step b).
Preferably, described emulsifying agent is the polyethenoxy ether class emulsifying agent.
Preferably, described protective colloid is polyvinyl alcohol.
Preferably, the weight ratio of described protective colloid, emulsifying agent, pH buffer reagent, oxygenant, reductive agent and Vinyl Acetate Monomer is (1～2): (0.5～2.5): (1～2): (0.1～2): (0.1～3): 100.
Preferably, the weight ratio of described protective colloid, emulsifying agent, pH buffer reagent, oxygenant, reductive agent and Vinyl Acetate Monomer is 1.5: (1～2.5): 1.5: (0.5～2): (0.5～2): 100.
Preferably, also comprise: add softening agent in the product that obtains to described polyreaction.
Preferably, described softening agent is lipid acid monooctyl ester, dioctyl phthalate (DOP), dibutyl phthalate, Octyl adipate, dioctyl sebacate or diethylene glycol dibenzoate.
The invention provides a kind of preparation method of film-forming agent for glass fiber injection yarn, may further comprise the steps: protective colloid, emulsifying agent, pH buffer reagent and water are mixed, obtain the first mixing solutions; In described the first mixing solutions, add Oxidizing and Reducing Agents, drip Vinyl Acetate Monomer, obtain film-forming agent for glass fiber injection yarn after the polyreaction.Compared with prior art, the present invention utilizes redox system to cause free-radical emulsion polymerization,, the free radical that redox reaction produces the energy initiated polymerization occurs between oxygenant and the reductive agent that is.Because this redox system reduces the activation energy that generates free radical greatly, improve polymerization rate and namely improve throughput, thereby improved the molecular weight of membrane-forming agent.Experimental result shows that the aqueous polyvinyl acetate emulsion molecular weight of the present invention's preparation uses the glass fibre of the membrane-forming agent of the method preparation to have good stiffness and cutting property 30000～80000.
Embodiment
The below is clearly and completely described the technical scheme in the embodiment of the invention, and obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The invention discloses a kind of preparation method of film-forming agent for glass fiber injection yarn, may further comprise the steps:
Step a) is mixed protective colloid, emulsifying agent, pH buffer reagent and water, obtains the first mixing solutions;
Step b) in described the first mixing solutions, adds Oxidizing and Reducing Agents, drip Vinyl Acetate Monomer, obtain film-forming agent for glass fiber injection yarn after the polyreaction, described reductive agent is iron protochloride, mercaptan, S-WAT or ferrous sulfate, and described oxygenant is hydrogen peroxide, t-butyl hydroperoxide, isopropyl benzene hydroperoxide or Sodium Persulfate.
The present invention utilizes redox system to cause free-radical emulsion polymerization, and the free radical that redox reaction produces the energy initiated polymerization occurs between oxygenant and the reductive agent, and obtaining film-forming agent for glass fiber injection yarn after the letex polymerization is acetate emulsion.
According to the present invention, described protective colloid preferably adopts polyvinyl alcohol, more preferably adopts polyvinyl alcohol 2488.Polyvinyl alcohol is a kind of water-soluble environment protective type high molecular polymer, and nontoxic pollution-free has good film forming properties, emulsifying property, adhesive property and spinning properties.The film that polyvinyl alcohol forms has excellent adhesion, solvent resistance, rub resistance, tensile strength and oxygen barrier performance.Because polyvinyl alcohol has hydrophilic group and two kinds of functional groups of hydrophobic group simultaneously, is the material with interfacial activity, therefore, the protective colloid when polyvinyl alcohol can be used as macromolecule emulsion, suspension polymerization.There is no particular restriction for the manufacturer of the polyvinyl alcohol that adopts in the present invention, the polyvinyl alcohol 2488 that preferably adopts fond dream good Chemical Industry Science Co., Ltd in Shanghai to produce.
Emulsifying agent is a class tensio-active agent, and effect is: form film or electrostatic double layer when emulsifying agent is dispersed in dispersate surperficial, can makes disperse phase with electric charge, thereby stop the small droplets of disperse phase to condense mutually, make the emulsion of formation more stable.The emulsifying agent that the present invention adopts preferably adopts the nonionogenic tenside that does not contain APE, more preferably adopts the polyethenoxy ether class emulsifying agent, more preferably fatty alcohol-polyoxyethylene ether.Fatty alcohol-polyoxyethylene ether be as ionic compound be a kind of oyster white paste to decorating film, wherein, the pH value of the aqueous solution of 1% fatty alcohol-polyoxyethylene ether is 5.0～7.0.There is no particular restriction for the manufacturer of the fatty alcohol-polyoxyethylene ether that adopts in the present invention, the fatty alcohol-polyoxyethylene ether that preferably adopts Haian County national power chemical industry company limited to produce.
When adding a certain amount of bronsted lowry acids and bases bronsted lowry in the solution, it is the pH buffer reagent that the reagent that hinders the effect that pH value of solution changes is arranged.The pH buffer reagent that the present invention adopts can be the mixing solutions of weak acid and salt thereof, and such as the mixing solutions of acetic acid (HAc) with sodium-acetate (NaAc), the perhaps mixing solutions of weak base and salt thereof is such as NH
3H
2O and NH
4The mixing solutions of Cl etc.Simultaneously, the pH buffer reagent that the present invention adopts can dispose voluntarily or be commercial, and there is no particular restriction for its manufacturer.
In addition, step a) in, each raw material is mixed to get the first mixing solutions after, preferably described the first mixing solutions is warming up to 50～62 ℃, more preferably be warming up to 55～60 ℃, more preferably be warming up to 60 ℃.After described the first mixing solutions intensification, in described the first mixing solutions, add Oxidizing and Reducing Agents, drip Vinyl Acetate Monomer and carry out polyreaction.Wherein, described Vinyl Acetate Monomer can adopt the mode that continues dropping, and is namely continual to described the first mixed solution and dripping Vinyl Acetate Monomer; Oxygenant preferably adopts the mode of disposable whole addings; Described reductive agent preferably adds after adding oxygenant, the preferred mode that adds or drip in batches that adopts.
Described step b) is specially: step b1) in described the first mixing solutions, add oxygenant; Step b2) to described step b1) drip Vinyl Acetate Monomer in the product that obtains, add reductive agent in batches, obtain film-forming agent for glass fiber injection yarn after the polyreaction, described reductive agent is iron protochloride, mercaptan, S-WAT or ferrous sulfate, and described oxygenant is hydrogen peroxide, t-butyl hydroperoxide, isopropyl benzene hydroperoxide or Sodium Persulfate.The temperature of polyreaction described step b2) is preferably 65～85 ℃, more preferably 70～85 ℃.In this step, take oxygenant as hydrogen phosphide cumene, reductive agent is Fe
2+Be example, at first carry out chain starting reaction, i.e. Oxidizing and Reducing Agents generation redox reaction generates a free radical, and then radical transfer is to Vinyl Acetate Monomer, and the reaction that generates free radical is as follows:
RC-OOH+Fe
2+→ RC
.+ OH
-+ Fe
3+, RC-OOH is hydrogen phosphide cumene, wherein RC
.Be free radical, i.e. C9H11O
.
Then carry out transfer reaction, begin polymerization with the monomer of free radical and other Vinyl Acetate Monomers and carry out chainpropagation; Chain termination reaction occurs at last, and namely two chains with living radical meet, and namely stop, and chainpropagation finishes, and forming glass fiber injection yarn is polyvinyl acetate emulsion with film forming.
Mainly contain at present two kinds of triggering mechanisms, the one, thermal initiation, the 2nd, redox.Thermal initiation refers to that under the effect of heat energy, the atom in the molecule can obtain very large vibrational energy, and when these energy were enough to overcome chemical bond energy, molecule will homolysis occur and produce free radical.But because the molecular weight of the film forming that thermal initiation forms, therefore, the present invention adopts redox system, changes the mechanism that generates free radical.Redox is the free radical that produces the energy initiated polymerization by between oxygenant and the reductive agent redox reaction occuring.Because redox system can reduce the activation energy that generates free radical greatly, so in the constant situation of reaction conditions, adopt redox system can improve polymerization rate, namely improve throughput.But, the dissociation constant of initiator system was large when temperature was higher, therefore, when guaranteeing certain throughput, the present invention has adopted lower temperature of reaction, namely adopt redox system and reduce polymeric reaction temperature, avoided the generating rate of free radical to cause greatly chain termination speed increase in emulsion particle, thereby avoided the molecular-weight average reduction.
As can be seen from the above analysis, because that redox system produces the needed energy of free radical is lower, redox system can reduce the activation energy that generates free radical greatly, for example, and take oxygenant as hydrogen phosphide cumene, reductive agent is Fe
2+For example activation energy is 50.7KJ/mol.Accordingly, the present invention has adopted lower temperature of reaction, has avoided the generating rate of free radical excessive, thereby avoided the quickening of the chain termination speed in the emulsion particle, has guaranteed that the molecular-weight average of membrane-forming agent of preparation is higher.In addition, the present invention has not only adopted suitable initiator system can guarantee that not only reaction normally carries out, and gives good use properties of emulsion later stage, and reduces the requirement to reaction conditions and production unit.
Cause the hard increase of film when the molecular weight of the membrane-forming agent that the present invention prepares increases, cohesiveness is good not, can increase adhesive property so add certain softening agent.Therefore, the present invention also comprises: add softening agent in the product that obtains to described polyreaction, described softening agent is preferably ester plasticizer, more preferably lipid acid monooctyl ester, dioctyl phthalate (DOP), dibutyl phthalate, Octyl adipate, dioctyl sebacate or diethylene glycol dibenzoate.There is no particular restriction for the manufacturer of the ester plasticizer that adopts in the present invention, the lipid acid monooctyl ester that preferably adopts the poly-source rich chemical industry company limited in Shijiazhuang to produce.This softening agent can reduce the low film formation temperature of emulsion, invests the good softness of emulsion, and cohesiveness etc. can reduce its volatility simultaneously, reduce the volatilization of objectionable impurities.Therefore, the present invention has increased the adhesive property of membrane-forming agent by having added a kind of environment protection type high-boiling-point softening agent, solved its volatile problem, guarantees that simultaneously it has suitable film-forming temperature.
The weight ratio prescription of the composition of each raw material that the present invention adopts has material impact to the performance of the film-forming agent for glass fiber injection yarn of preparation.The weight ratio of described protective colloid, emulsifying agent, pH buffer reagent, oxygenant, reductive agent and Vinyl Acetate Monomer is preferably (1～2): (0.5～2.5): (1～2): (0.1～2): (0.1～3): 100, more preferably 1.5: (1～2.5): 1.5: (0.5～2): (0.5～2): 100.Wherein, the emulsifier concentration that the present invention adopts is moderate, when one timing of free radical generating rate, the quantity of emulsion particle is larger, the mean lifetime of free radical in emulsion particle is just longer, thereby free radical just has the sufficient time to carry out chainpropagation, so it can reach very large molecular weight Mn.When but emulsifier concentration was excessive, emulsion particle diameter can diminish, and caused in glass is produced the emulsion utilization ratio not high.Simultaneously, comparatively fast molecular weight is also large as much as possible simultaneously for its speed of reaction of the moderate assurance of initiator concentration.
In sum, the present invention fills a prescription by adjusting, technology optimization goes out a kind of polyvinyl acetate emulsion, and this emulsion is cheap, and cohesiveness is strong, gives the good stiffness of precursor and cutting.The molecular weight of the aqueous polyvinyl acetate emulsion that is synthesized by this composition and engineering is larger, and about 30000～80000, its high molecular has given glass fiber product good stiffness and cutting property just.In addition, the present invention preferably adds the environment protection type high-boiling-point softening agent, and it is higher to have solved cost, and adhesive property is bad, the problems such as volatile not environmental protection.
In order to further specify technical scheme of the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The chemical reagent that the embodiment of the invention and comparative example adopt is commercial.
Embodiment 1
Be prepared into film according to the described proportioning raw materials of table 1.
Protective colloid: polyvinyl alcohol;
Emulsifying agent: fatty alcohol-polyoxyethylene ether;
The pH buffer reagent: the upper graceful bio tech ltd pH of Hypon is 6.86;
Oxygenant: isopropyl benzene hydroperoxide;
Reductive agent: iron protochloride.
1, take by weighing an amount of reductive agent, add entry and be configured to 10% reductant solution, it is for subsequent use to take by weighing simultaneously Vinyl Acetate Monomer 8g;
2, take by weighing respectively 1.5g protective colloid, emulsifying agent, 1.5g pH buffer reagent and water in the glass reaction still;
3, put up condensation reflux unit, be warmed up to 60 ℃, in still, add an amount of oxygenant, continue to be warming up to 65～85 ℃;
4, insulation reaction after temperature reaches 65～85 ℃ adds the 1/4 above-mentioned reductant solution of preparing, the Vinyl Acetate Monomer that begins to drip with pump above-mentioned preparation, and the rate of addition of adjusting monomer guarantees that monomer can dropwise at 15～20min, insulation 30min;
5, insulation finishes, and adds the reductant solution of 8% above-mentioned preparation, then takes by weighing the 92g Vinyl Acetate Monomer, drips with pump, regulates the rate of addition of monomer, guarantees that monomer can dropwise in 4～4.5h;
6, the reductant solution that adds 8% above-mentioned preparation every 30min;
7, when the remaining reductant solution of the complete adding of monomer dropping, and add an amount of softening agent in still, plasticising 30min, cooling discharge, obtaining polyvinyl acetate emulsion is film-forming agent for glass fiber injection yarn.
The molecular weight of the film-forming agent for glass fiber injection yarn of present embodiment preparation is 30000～80000.
Embodiment 2～3
According to the described proportioning raw materials of table 1, adopt the preparation method of embodiment 1, preparing polyvinyl acetate emulsion is film-forming agent for glass fiber injection yarn.
The molecular weight of the film-forming agent for glass fiber injection yarn of embodiment 2～3 preparations is respectively 30000～80000.
The proportioning raw materials that table 1 embodiment 1～3 adopts
Comparative example 1
1, be prepared into film by the proportioning raw materials shown in the table 2, take by weighing the thermal initiator that an amount of Shenzhen Kai Ji Applied Materials Inc produces, add the solution that entry is configured to 10% thermal initiator, it is for subsequent use to take by weighing simultaneously Vinyl Acetate Monomer 8g;
2, take by weighing respectively 1.5g protective colloid, emulsifying agent, 1.5g pH buffer reagent and water in the glass reaction still;
3, put up condensation reflux unit, be warming up to 65～85 ℃;
4, insulation reaction after temperature reaches 65～85 ℃, add the 1/4 above-mentioned thermal initiator solution of preparing, the Vinyl Acetate Monomer that begins to drip with pump above-mentioned preparation, the rate of addition of adjusting monomer, guarantee that monomer can dropwise at 15～20min, insulation 30min;
5, insulation finishes, and adds the thermal initiator solution of 8% above-mentioned preparation, then takes by weighing the 92g Vinyl Acetate Monomer, drips with pump, regulates the rate of addition of monomer, guarantees that monomer can dropwise in 4～4.5h;
6, the thermal initiator solution that adds 8% above-mentioned preparation every 30min;
7, when the remaining thermal initiator solution of the complete adding of monomer dropping, and add an amount of softening agent in still, plasticising 30min, cooling discharge, obtaining polyvinyl acetate emulsion is film-forming agent for glass fiber injection yarn.
The proportioning raw materials that table 2 comparative example 1 adopts
The composition for the treatment of compound:
The lubricant of the membrane-forming agent of the present invention of 10wt%, the silane coupling agent of 0.2～0.4wt%, 0.2～0.5wt%, the static inhibitor of 0.1～0.3wt%, the pH adjusting agent of 0.1～0.2wt and the water of 88.7～89.4wt%.
Soak and join process:
Join in the filling soaking first, add the water of 50wt%, open stirring, slowly add membrane-forming agent.Added and stirred among the 30min, slowly added successively silane coupling agent, lubricant, static inhibitor; Add at last the pH agent, pH is adjusted to suitable scope both obtained treating compound.
Film-forming agent for glass fiber injection yarn to the embodiment of the invention 1～3 and comparative example 1 preparation carries out Performance Detection, and method is as follows:
1, at first adjusts air pressure, glass fiber content is adjusted to 30 ± 2%;
2, readiness tray package paper dividing plate is divided into two, hard template of spraying as facade on the wall;
3, with the normal yarn of R10VC as the test standard specimen, sprayed respectively 30 seconds, 35 seconds, 40 seconds, choose suitable injecting time as the experiment yarn the injection standard times;
4, to spray standard times injections that be as the criterion, repeat step 2 with the experiment yarn, after the record injection is finished, the situation of the yarn that collapses.The same time, the yarn that collapses is more, and effect is poorer; The yarn that collapses is fewer, and jeting effect is better.
Observing by experiment us finds: 35 seconds injecting time is proper, because substantially do not collapse yarn in 25 seconds, the yarn that collapses was apparent in view in 40 seconds, 35 seconds yarns that slightly collapse.So we choose 35 seconds for spraying the standard times.
Three times prescription is tested, find: use the jeting effect of R10VC of membrane-forming agent of the embodiment of the invention 1～3 preparation better, uses the jeting effect of R10VC of the membrane-forming agent that comparative example 1 of the present invention prepares relatively poor.And the jeting effect of the R10VC of the membrane-forming agent of the use embodiment of the invention 1～3 preparation all is better than the normal yarn of standard R10VC, and the yarn situation that collapses is all lacked than the normal yarn of R10VC.
The R10VC of the membrane-forming agent of the above-mentioned use embodiment of the invention 1～3, comparative example 1 preparation and the performance of normal R10VC are detected, and detected result is as shown in table 3.
The results of property of the glass fiber injection yarn of table 3 the present invention preparation
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can in the situation that does not break away from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. the preparation method of a film-forming agent for glass fiber injection yarn may further comprise the steps:
Step a) is mixed protective colloid, emulsifying agent, pH buffer reagent and water, obtains the first mixing solutions;
Step b) adds Oxidizing and Reducing Agents in described the first mixing solutions, drip Vinyl Acetate Monomer, obtain film-forming agent for glass fiber injection yarn after the polyreaction, described reductive agent is iron protochloride, mercaptan, S-WAT or ferrous sulfate, and described oxygenant is hydrogen peroxide, t-butyl hydroperoxide, isopropyl benzene hydroperoxide or Sodium Persulfate;
The weight ratio of described protective colloid, emulsifying agent, pH buffer reagent, oxygenant, reductive agent and Vinyl Acetate Monomer is (1～2): (0.5～2.5): (1～2): (0.1～2): (0.1～3): 100.
2. preparation method according to claim 1 is characterized in that, described step b) is specially:
Step b1) in described the first mixing solutions, adds oxygenant;
Step b2) to described step b1) drip Vinyl Acetate Monomer in the product that obtains, add reductive agent in batches, obtain film-forming agent for glass fiber injection yarn after the polyreaction, described reductive agent is iron protochloride, mercaptan, S-WAT or ferrous sulfate, and described oxygenant is hydrogen peroxide, t-butyl hydroperoxide, isopropyl benzene hydroperoxide or Sodium Persulfate.
3. preparation method according to claim 2 is characterized in that, described step b2) the temperature of polyreaction be 65～85 ℃.
4. preparation method according to claim 1 is characterized in that, reductive agent adds the dropping mode that adopts in the described step b).
5. preparation method according to claim 1 is characterized in that, described emulsifying agent is the polyethenoxy ether class emulsifying agent.
6. preparation method according to claim 1 is characterized in that, described protective colloid is polyvinyl alcohol.
7. preparation method according to claim 1; it is characterized in that the weight ratio of described protective colloid, emulsifying agent, pH buffer reagent, oxygenant, reductive agent and Vinyl Acetate Monomer is 1.5:(1～2.5): 1.5:(0.5～2): (0.5～2): 100.
8. preparation method according to claim 1 is characterized in that, also comprises:
Add softening agent in the product that obtains to described polyreaction.
9. preparation method according to claim 8 is characterized in that, described softening agent is lipid acid monooctyl ester, dioctyl phthalate (DOP), dibutyl phthalate or diethylene glycol dibenzoate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210016030 CN102532371B (en) | 2012-01-18 | 2012-01-18 | Preparation method of film-forming agent for glass fiber injection yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210016030 CN102532371B (en) | 2012-01-18 | 2012-01-18 | Preparation method of film-forming agent for glass fiber injection yarn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102532371A CN102532371A (en) | 2012-07-04 |
| CN102532371B true CN102532371B (en) | 2013-10-16 |
Family
ID=46340516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210016030 Active CN102532371B (en) | 2012-01-18 | 2012-01-18 | Preparation method of film-forming agent for glass fiber injection yarn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102532371B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558366A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工集团公司 | Cationic polyvinyl acetate emulsion as well as synthesis method and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558320B (en) * | 2014-12-30 | 2017-02-22 | 巨石集团有限公司 | Polyvinyl acetate emulsion |
| CN105601774B (en) * | 2016-02-19 | 2017-11-03 | 常州天马集团有限公司（原建材二五三厂） | Fiberglas chopped strand mat emulsion binder and preparation method thereof |
| CN106188426B (en) * | 2016-07-15 | 2018-11-02 | 巨石集团有限公司 | A kind of film-forming agent for glass fiber injection yarn and preparation method thereof |
| CN109485274B (en) * | 2018-12-27 | 2022-02-01 | 巨石集团有限公司 | Impregnating compound for high-speed jet molding of glass fiber and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807471A (en) * | 2005-01-20 | 2006-07-26 | 常德市金芙蓉精细化工有限责任公司 | Vinyl acetate based high viscosity latex preparation method |
| CN102040790A (en) * | 2009-08-18 | 2011-05-04 | 中国科学院成都有机化学有限公司 | Fireproof polyvinyl acetate emulsion and preparation method thereof |
-
2012
- 2012-01-18 CN CN 201210016030 patent/CN102532371B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807471A (en) * | 2005-01-20 | 2006-07-26 | 常德市金芙蓉精细化工有限责任公司 | Vinyl acetate based high viscosity latex preparation method |
| CN102040790A (en) * | 2009-08-18 | 2011-05-04 | 中国科学院成都有机化学有限公司 | Fireproof polyvinyl acetate emulsion and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558366A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工集团公司 | Cationic polyvinyl acetate emulsion as well as synthesis method and application thereof |
| CN104558366B (en) * | 2013-10-22 | 2017-01-04 | 中国石油化工集团公司 | A kind of cationic polyvinyl acetates ester emulsion and preparation method and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102532371A (en) | 2012-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102532371B (en) | Preparation method of film-forming agent for glass fiber injection yarn | |
| CN103864982B (en) | Preparation method of fluorinated acrylate emulsion | |
| CN101367898B (en) | PVDC copolymerization emulsion, preparation and uses thereof | |
| CN102153971B (en) | Waterborne aluminium foil adhesive and preparation method thereof | |
| CN103045113B (en) | Preparation method of self-crosslinking IPN (interpenetrating network) organosilicone-acrylate copolymer emulsion pressure-sensitive adhesive | |
| CN101531745B (en) | Preparation of plural gel water absorbent material composed of silk fibroin/acrylic acid/acrylamide | |
| CN105385389B (en) | A kind of super water-fast two-component splicing adhesive of environmental protection and preparation method thereof | |
| CN106519594B (en) | A kind of PBT engineering plastic compositions of oil rub resistance hydrolysis and preparation method thereof for nanometer injection molding | |
| CN102086360A (en) | Modified starch-based wood adhesive as well as preparation method and application thereof | |
| CN101906278A (en) | Single-component polyvinylacetate binding agent and preparation method thereof | |
| CN104789167A (en) | High-temperature-resistant adhesive tape as well as high-temperature-resistant release film and high-temperature-resistant adhesive used by high-temperature-resistant adhesive tape | |
| CN112251174B (en) | Environment-friendly water-based composite adhesive and preparation method thereof | |
| CN103483491A (en) | Carbomer and preparation method thereof | |
| CN107417861A (en) | A kind of preparation method of salt tolerance water shutoff agent | |
| CN104558320B (en) | Polyvinyl acetate emulsion | |
| CN112126389A (en) | Plasticizer migration resistant aqueous pressure-sensitive adhesive and preparation method thereof | |
| CN103665241A (en) | Cationic ethylene-vinyl acetate copolymer emulsion and production method thereof | |
| CN109233728A (en) | A kind of Epoxy Resin Acrylate copolymerization pressure sensitive adhesive and preparation method thereof | |
| CN102627741B (en) | Preparation method of fluoride silicon macromolecular emulsion modified acrylic ester emulsion | |
| CN1139643C (en) | Flexible coatings with low surface tack and surface tension | |
| CN109988322A (en) | Water-based fluoropolymer emulsion, preparation method and applications | |
| CN113754834A (en) | Super-hydrophobic stain-resistant emulsion and preparation method thereof | |
| CN109331544A (en) | A kind of polyethylene filter core of persistent hydrophilic modification and preparation method thereof | |
| CN106832085A (en) | A kind of high temperature resistant, high rigidity acrylate and vinyl acetate emulsion of color inhibition and preparation method thereof | |
| CN104974695A (en) | Vinyl acetate-soybean protein copolymer emulsion timber adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 400082 Dadukou District of Chongqing Bridge Industrial Park B District Patentee after: Chongqing international composite Limited by Share Ltd Address before: 400082 Chongqing Polycomp International Corporation Dadukou District of Chongqing Bridge Industrial Park B District Patentee before: Chongqing Polycomp International Corp. |