CN105384878A - Powder amylbenzene rubber and preparation method thereof - Google Patents
Powder amylbenzene rubber and preparation method thereof Download PDFInfo
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- CN105384878A CN105384878A CN201511030221.4A CN201511030221A CN105384878A CN 105384878 A CN105384878 A CN 105384878A CN 201511030221 A CN201511030221 A CN 201511030221A CN 105384878 A CN105384878 A CN 105384878A
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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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
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Abstract
The invention provides powder amylbenzene rubber. The powder amylbenzene rubber is mainly prepared from the following components: 27 to 36 percent of comonomer, 9 to 18 percent of grafted monomer, 0.18 to 0.23 percent of initiating agent, 0.4 to 0.68 percent of emulsifying agent and the balance of water, wherein the comonomer at least comprises isoprene and styrene, the grafted monomer comprises styrene and acrylonitrile. Polyvinyl chloride is modified through the powder amylbenzene rubber, so that the shock resistance and tensile property are improved. In addition, the invention also relates to a preparation method of the powder amylbenzene rubber. The preparation method has the characteristics of simple process, high production efficiency and the like.
Description
Technical field
The present invention relates to rubber production field, in particular to a kind of powder penta benzene rubber and preparation method thereof.
Background technology
Along with improving constantly of scientific and technological level, expand also more and more being subject to people's attention of elastomeric Application Areas.Simultaneously, the exploitation of rubberresin blends, modified cement, modifying asphalt etc. and applied research is adopted also to rise gradually.But due to cohesive force and the snappiness of rubber itself, be difficult to Homogeneous phase mixing with the said products, so do not reach the desired result of modification.In addition, this needs stripping and slicing, mixing in the course of processing also to there is niggerhead, the problems such as troublesome poeration, labour intensity are large, so last century, early seventies developed countries began one's study fluid rubber and powdered rubber, define suitability for industrialized production thereafter gradually.
Powdered rubber has plurality of advantages compared with niggerhead, and such as, easily mix with the plastics be modified, cement, pitch etc., modified effect is good.In addition, use powdered rubber to cancel and cut adhesive process, shorten mixing cycle, reduce energy consumption, reduce labor intensity.By being blended into powdered rubber masterbatch with other carbon black, fleut, directly rubber item etc. can be processed into.
From the seventies later stage, synthetic rubber and the polymer processing enterprise of the developed countries such as the U.S., Germany, Britain, Japan are all being devoted to the research, development and production of rubber powder.Wherein producing maximum is powdered nitrile rubber, and be secondly powder butylbenzene, main application is modified plastics and cement, pitch etc.Also do not see at present about preparing the relevant report that can be used as the powder penta benzene rubber of modified additive.
Summary of the invention
The first object of the present invention is to provide a kind of powder penta benzene rubber, and it has better mechanical property.
The second object of the present invention is the preparation method providing a kind of powder penta benzene rubber, and it has, and technical process is simple, production efficiency advantages of higher.
In order to realize above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind of powder penta benzene rubber, is made primarily of following component: by weight,
Described comonomer at least comprises isoprene and vinylbenzene, and described isoprene and described cinnamic weight ratio are 2:1 ~ 5:1;
Described grafted monomer comprises vinylbenzene and vinyl cyanide, and the weight ratio of described vinylbenzene and described vinyl cyanide is 3:2 ~ 2:3;
Described initiator comprise in Potassium Persulphate, Sodium Persulfate, ammonium persulphate one or more, described emulsifying agent comprised sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, one or more in sodium laurylsulfonate.
This powder penta benzene rubber is that side chain makes the graft copolymer formed using isoprene and vinylbenzene as main chain, with vinylbenzene and vinyl cyanide.Grafting process reduce obtained powder penta benzene rubber melt viscosity, improve its mobility, be conducive to carrying out secondary processing to powder penta benzene rubber.In addition, the activation point of the powder penta benzene rubber after grafting is more, is more conducive to interact with other compositions such as rubber, plastics, thus can forms the polymkeric substance of high molecular under relatively mild condition, to improve the performance of the product such as rubber, plastics.The existence of side chain makes the spatial arrangement of the molecule segment of powder penta benzene rubber more tight, and its size is less, can reduce the particle diameter of product, is convenient to and other mixing of materials.
Persulphate has higher solubleness in water, can produce the persulfate ion with strong oxidation.Persulfate ion is hankered producing radical polymerization in aqueous systems.Persulfate initiator causes emulsion polymerization under being suitable for cold condition, can avoid the problem causing reaction system poor stability because letex polymerization temperature is too high.Pyroreaction can cause the emulsion particle pedesis in reaction system to aggravate, thus makes latex particle mutually collide polymerization, causes the stable decline of reaction system.In addition, pyroreaction easily causes monomer implode, and then the problem such as structure deteriorate, loss of product occurs.The emulsifying agent of above-mentioned dodecane base system is anion surface activity composition, it has good solubleness in water, strong to the emulsifying effect of comonomer, grafted monomer, can promote that comonomer, grafted monomer are scattered in aqueous systems fully, be beneficial to and obtain particle diameter less powder penta benzene rubber.
Above-mentioned powder penta benzene rubber outward appearance is white powder, and apparent density is at 0.4g/cm
3above, the content of 1000 μm of screeningss is below 1%.The polymerization degree of 100 weight parts be 1000 polyvinyl chloride and 20 parts by weight of powder penta benzene blend rubbers after, tensile strength is at more than 17MPa, and resistance to impact shock is at 9KJ/m
2above, breaking tenacity is at more than 17MPa, and elongation is more than 250%.
Preferably, described comonomer also comprises: vinyl monomer, and/or unsaturated fatty acids alkyl esters monomer, and the consumption of described vinyl monomer and described unsaturated fatty acids alkyl esters monomer accounts for less than 20% of described comonomer gross weight.
Adding of vinyl monomer and full, fatty acid alkyl ester class monomer, the quantity in the active centre of comonomer polymerization after product can be improved, to be polymerized with grafted monomer more fully.
Preferably, described vinyl monomer comprises one or more in divinyl, vinyl toluene, ethyl styrene.
Vinyl monomer can be powder penta benzene rubber and provides vinyl, thus improves the intermiscibility between powder penta benzene rubber and the material with vinyl, and then reduces the manufacture difficulty of modified product.
Preferably, described unsaturated fatty acids alkyl esters monomer comprises one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl methyl acrylate, ETHYL HEXYL ACRYLATE, butyl methacrylate.
Unsaturated fatty acids acid alkyl ester has plastification, can reduce melt viscosity and the yield temperature of obtained powder penta benzene rubber, is convenient to carry out secondary processing to powder penta benzene rubber.The unsaturated fatty acids of esterified with alkyl, acid reduces, the elevation of boiling point and not volatile, makes polymerization process controllability higher.
The preparation method of above-mentioned powder penta benzene rubber, comprises the following steps:
A) water, comonomer, initiator, emulsifying agent are joined in reactor and be mixed to form polymeric solution, described polymeric solution reacts 10 ~ 15 hours under 50 ~ 70 DEG C of conditions, obtain latex, the consumption of described water is 1.2 ~ 1.5 times of described comonomer weight, the consumption of described initiator is 0.4 ~ 0.6% of described comonomer weight, and the consumption of described emulsifying agent is 1 ~ 2% of described comonomer weight;
B) described latex, grafted monomer and remaining water, remaining initiator, remaining emulsifying agent are mixed in reactor and form graft copolymer solution, described graft copolymer solution reacts 2 ~ 4 hours under 50 ~ 70 DEG C of conditions, obtain graft emulsion, then spraying dry, to obtain final product.
First, obtain isoprene and cinnamic multipolymer by such as letex polymerization, then, with this multipolymer for main chain carries out graft polymerizing styrene and vinyl cyanide side chain, thus prepare graft copolymer.This preparation method is by two polymerization procedure, then drying can obtain powdered rubber.Emulsion polymerization system easy heat radiation, avoids hot polymerization collection in polymerization process, thus reduces the situation that implode occurs, and reduces the difficulty of thermal control simultaneously.The viscosity of emulsion polymerization systems is low, mobility is high, is more conducive to make.Aqueous based systems, makes polymerization process safely, reliably.Spraying dry passes through liquid material ejection at a high speed, drying, and can obtain powder-product, its efficiency is high, easy and simple to handle.Due in drying process, rubber molecule does not bear larger shearing action, and the integrity degree of its molecular chain is high, more easily and other modification material mixing.
Preferably, steps A) in, when described mixing, also add ionogen, described ionogen comprises phosphoric acid salt, and described electrolytical weight is 0.3 ~ 0.8% of described comonomer weight.
Ionogen prevents from contacting with each other between the multipolymer in reaction system, boning, and can reduce the viscosity of reaction system, improve mobility, to be uniformly mixed reaction soln, make polyreaction more abundant.
Preferably, described phosphoric acid salt comprises potassiumphosphate, and/or sodium phosphate.
Preferably, step B) in, after obtaining graft emulsion, before spraying dry, also comprise: in described graft emulsion, add weighting agent, and/or antioxidant, the weight of described weighting agent is 10 ~ 20% of the weight sum of described grafted monomer and described comonomer, and the total amount of described antioxidant is 0.4 ~ 0.6% of the weight sum of described grafted monomer and described comonomer.
Weighting agent and antioxidant can be used as the performance improving the finished product.Wherein, weighting agent can reduce the dry difficulty in making processes, improves rate of drying; Antioxidant then can improve the antioxidant property of obtained powdered rubber, delays the ager process of powdered rubber, improves work-ing life.
Preferably, described weighting agent comprises titanium dioxide, and/or calcium carbonate; Described antioxidant comprise in antioxidant 1076, antioxidant 2246, oxidation inhibitor 4720 one or more.
Preferably, described calcium carbonate is light calcium carbonate.
Preferably, step B) in, after obtaining graft emulsion, before spraying dry, also comprise: in described graft emulsion, add dispersion agent, described dispersion agent to comprise in styrene-maleic anhydride copolymer, polyvinyl alcohol, gelatin, Walocel MT 20.000PV, calcium stearate, lead stearate, Zinic stearas one or more, and the consumption of described dispersion agent is 3 ~ 5% of the weight of described grafted monomer.
Dispersion agent can prevent polymer particle adhesion each other, reduces the particle diameter of obtained powdered rubber.Styrene-maleic anhydride copolymer, polyvinyl alcohol, gelatin, Walocel MT 20.000PV can avoid graftomer mutually to bond in reaction system, thus lower the viscosity of reaction system, and solution more easily disperses, and improves drying property, more easily forms powdery.Calcium stearate, lead stearate, Zinic stearas then have lubrication, and the rubbing effect after reduction grafting between rubber particles, makes the mobility of reaction system improve, more easily carry and disperse.
Preferably, described spray-dired temperature in is 130 ~ 140 DEG C.
Dry at such a temperature, the moisture rapid evaporation in solution can be made, reduce time of drying, avoid that powdered rubber heated time is oversize or temperature is too high and produce aging problem.
Beneficial effect of the present invention: powder penta benzene rubber provided by the invention can be used as modified additive and carries out modification to materials such as rubber, plastics, pitches, has good toughening effect.Powder penta benzene rubber has good mobility, not easily lumps, and pipeline can be utilized to transport in storage and transportation, and therefore, the use of penta benzene rubber of powdered can improve automatization and the production efficiency of modified product production.Intermiscibility between penta benzene rubber of collateralization and modification material is high, can reduce the mixing difficulty between penta benzene rubber and modification material.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting the scope of the invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturers suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, be and can buy by commercially available the conventional products obtained.
Embodiment 1
Present embodiments provide a kind of powder penta benzene rubber, comprise following component:
Comonomer 800 grams; Grafted monomer 200 grams; Initiator 4 grams; Emulsifying agent 10 grams; 1200 grams, water.
Wherein, comonomer comprises isoprene and vinylbenzene, and isoprene and cinnamic weight ratio are 4:1; Grafted monomer comprises vinylbenzene and vinyl cyanide, and the weight ratio of vinylbenzene and vinyl cyanide is 3:2; Initiator comprises Potassium Persulphate, and emulsifying agent comprised sodium lauryl sulphate.
Being made by the following method of above-mentioned powder penta benzene rubber:
Step 1,960 grams of water, 800 grams of comonomers, 3.2 grams of initiators, 8 grams of emulsifying agents are joined in reactor and be mixed to form polymeric solution, polymeric solution reacts 10 hours under 50 DEG C of conditions, obtains latex;
Step 2, latex, 240 grams of water, 200 grams of grafted monomer, 0.8 gram of initiator, 2 grams of emulsifying agents are mixed in reactor and form graft copolymer solution, graft copolymer solution reacts 2 hours under 50 DEG C of conditions, obtains graft emulsion, then dry, to obtain final product.
Embodiment 2
Present embodiments provide a kind of powder penta benzene rubber, comprise following component:
Comonomer 600 grams; Grafted monomer 400 grams; Initiator 4 grams; Emulsifying agent 10 grams; 1200 grams, water.
Wherein, comonomer comprises isoprene and vinylbenzene, and isoprene and cinnamic weight ratio are 5:1; Grafted monomer comprises vinylbenzene and vinyl cyanide, and the weight ratio of vinylbenzene and vinyl cyanide is 2:3; Initiator comprises Sodium Persulfate, and emulsifying agent comprised Sodium dodecylbenzene sulfonate.
Being made by the following method of above-mentioned powder penta benzene rubber:
Step 1,720 grams of water, 600 grams of comonomers, 2.4 grams of initiators, 6 grams of emulsifying agents are joined in reactor and be mixed to form polymeric solution, polymeric solution reacts 12 hours under 65 DEG C of conditions, obtains latex;
Step 2, latex, 480 grams of water, 400 grams of grafted monomer, 1.6 grams of initiators, 4 grams of emulsifying agents are mixed in reactor and form graft copolymer solution, graft copolymer solution reacts 2 hours under 60 DEG C of conditions, obtains graft emulsion, then dry, to obtain final product.
Embodiment 3
Present embodiments provide a kind of powder penta benzene rubber, comprise following component:
Comonomer 700 grams; Grafted monomer 300 grams; Initiator 6 grams; Emulsifying agent 20 grams; 1560 grams, water.
Wherein, comonomer comprises isoprene and vinylbenzene, and isoprene and cinnamic weight ratio are 9:2; Grafted monomer comprises vinylbenzene and vinyl cyanide, and the weight ratio of vinylbenzene and vinyl cyanide is 1:1; Initiator comprises ammonium persulphate, and emulsifying agent comprised sodium laurylsulfonate.
Being made by the following method of above-mentioned powder penta benzene rubber:
Step 1,1050 grams of water, 700 grams of comonomers, 4.2 grams of initiators, 14 grams of emulsifying agents are joined in reactor and be mixed to form polymeric solution, polymeric solution reacts 15 hours under 70 DEG C of conditions, obtains latex;
Step 2, latex, 510 grams of water, 300 grams of grafted monomer, 1.8 grams of initiators, 6 grams of emulsifying agents are mixed in reactor and form graft copolymer solution, graft copolymer solution reacts 4 hours under 70 DEG C of conditions, obtains graft emulsion, then dry, to obtain final product.
Embodiment 4
Present embodiments provide a kind of powder penta benzene rubber, comprise following component:
Comonomer 750 grams; Grafted monomer 260 grams; Initiator 5.3 grams; Emulsifying agent 14 grams; 1339 grams, water.
Wherein, comonomer comprises isoprene and vinylbenzene, and isoprene and cinnamic weight ratio are 21:5; Grafted monomer comprises vinylbenzene and vinyl cyanide, and the weight ratio of vinylbenzene and vinyl cyanide is 6:5; Initiator comprises ammonium persulphate, and emulsifying agent comprised sodium laurylsulfonate.
Being made by the following method of above-mentioned powder penta benzene rubber:
Water, 750 grams of comonomers, 3.8 grams of initiators, 9.8 grams of emulsifying agents join in reactor and are mixed to form polymeric solution by step 1,975, and polymeric solution reacts 13 hours under 54 DEG C of conditions, obtains latex;
Step 2, latex, 364 grams of water, 260 grams of grafted monomer, 1.5 grams of initiators, 4.2 grams of emulsifying agents are mixed in reactor and form graft copolymer solution, graft copolymer solution reacts 3 hours under 67 DEG C of conditions, obtains graft emulsion, then dry, to obtain final product.
Embodiment 5
Present embodiments provide a kind of powder penta benzene rubber, comprise following component:
Comonomer 530 grams; Grafted monomer 243 grams; Initiator 3.7 grams; Emulsifying agent 11.7 grams; 785 grams, water; Potassiumphosphate 2.5 grams; 77.3 gram calcium carbonate; 3 grams of antioxidant 1076s; Styrene-maleic anhydride copolymer 4.6 grams.
Wherein, comonomer comprises isoprene, vinylbenzene and butyl acrylate, and the weight ratio of isoprene, vinylbenzene and butyl acrylate is 65:25:10; Grafted monomer comprises vinylbenzene and vinyl cyanide, and the weight ratio of vinylbenzene and vinyl cyanide is 3:2; Initiator comprises ammonium persulphate, and emulsifying agent comprised sodium laurylsulfonate.
Being made by the following method of above-mentioned powder penta benzene rubber:
Step 1,742 grams of water, 530 comonomers, 3 grams of initiators, 9 grams of emulsifying agents, 2.5 grams of potassiumphosphates are joined in reactor and be mixed to form polymeric solution, polymeric solution reacts 13 hours under 54 DEG C of conditions, obtains latex;
Step 2, latex, 243 grams of water, 152 grams of grafted monomer, 0.7 gram of initiator, 2.7 grams of emulsifying agents, 4.6 grams of styrene-maleic anhydride copolymers are mixed in reactor and form graft copolymer solution, graft copolymer solution reacts 3 hours under 67 DEG C of conditions, obtain graft emulsion to mix with calcium carbonate and antioxidant 1706 again, then drying is carried out by spray-drying tower, spray-dired temperature in is 130 DEG C, to obtain final product.The styrene-maleic anhydride copolymer number-average molecular weight used in the present embodiment is 5000.
Embodiment 6
Present embodiments provide a kind of powder penta benzene rubber, comprise following component:
Comonomer 500 grams; Grafted monomer 227 grams; Cause 3.9 grams; Emulsifying agent 13.3 grams; 1013 grams, water; Sodium phosphate 4 grams; Light calcium carbonate 154 grams; 4.4 grams of antioxidant 2246s; Styrene-maleic anhydride copolymer 11.4 grams.
Wherein, comonomer comprises isoprene, vinylbenzene and divinyl, and the weight ratio of isoprene, vinylbenzene and divinyl is 65:25:10; Grafted monomer comprises vinylbenzene and vinyl cyanide, and the weight ratio of vinylbenzene and vinyl cyanide is 3:2; Initiator comprises Sodium Persulfate, and emulsifying agent comprised sodium lauryl sulphate.
Being made by the following method of above-mentioned powder penta benzene rubber:
Step 1,650 grams of water, 500 grams of comonomers, 2.9 grams of initiators, 9 grams of emulsifying agents, 4 grams of sodium phosphates are joined in reactor and be mixed to form polymeric solution, polymeric solution reacts 13 hours under 54 DEG C of conditions, obtains latex;
Step 2, latex, 363 grams of water, 227 grams of grafted monomer, 1 gram of initiator, 4.3 grams of emulsifying agents, 11.4 grams of styrene-maleic anhydride copolymers are mixed in reactor and form graft copolymer solution, graft copolymer solution reacts 3 hours under 67 DEG C of conditions, obtain graft emulsion to mix with light calcium carbonate and antioxidant 2246 again, then drying is carried out by spray-drying tower, spray-dired temperature in is 140 DEG C, to obtain final product.In the present embodiment, the molecular weight of styrene-maleic anhydride copolymer is 6000.
Embodiment 7
Present embodiments provide a kind of powder penta benzene rubber, comprise following component:
Comonomer 630 grams; Grafted monomer 340 grams; Initiator 4.8 grams; Emulsifying agent 12.6 grams; 1479 grams, water; Sodium phosphate 3.8 grams; Titanium dioxide 155 grams; 4.9 grams of antioxidant 2246s; Walocel MT 20.000PV 13.6 grams.
Wherein, comonomer comprises isoprene, vinylbenzene and divinyl, and the weight ratio of isoprene, vinylbenzene and divinyl is 65:25:10; Grafted monomer comprises vinylbenzene and vinyl cyanide, and the weight ratio of vinylbenzene and vinyl cyanide is 3:2; Initiator comprises Sodium Persulfate, and emulsifying agent comprised sodium lauryl sulphate.
Being made by the following method of above-mentioned powder penta benzene rubber:
Step 1,901 grams of water, 630 grams of comonomers, 3.2 grams of initiators, 8.2 grams of emulsifying agents, 3.8 grams of sodium phosphates are joined in reactor and be mixed to form polymeric solution, polymeric solution reacts 13 hours under 63 DEG C of conditions, obtains latex;
Step 2, latex, 578 grams of water, 340 grams of grafted monomer, 1.6 grams of initiators, 4.4 grams of emulsifying agents, 13.6 grams of Walocel MT 20.000PVs are mixed in reactor and form graft copolymer solution, graft copolymer solution reacts 3.5 hours under 55 DEG C of conditions, obtain graft emulsion to mix with titanium dioxide and antioxidant 2246 again, then drying is carried out by spray-drying tower, spray-dired temperature in is 137 DEG C, to obtain final product.
Test example 1
Powder penta benzene rubber powder styrene butadiene rubber on market, Powdered acrylonitrile-butadiene rubber and the embodiment of the present invention 1 to embodiment 7 (numbering 1-7 is one_to_one corresponding embodiment 1 to 7 respectively) provided is for modified polyvinyl chloride (polymerization degree is 1000), modification result is as shown in table 1, wherein powder styrene butadiene rubber is bought from Shandong Sheng Ya Chemical Co., Ltd., and production code member is 33010245016; Powdered acrylonitrile-butadiene rubber is bought from Shandong Sheng Ya Chemical Co., Ltd., and product type is PNBR-01.The method of modification is as hereafter.
Modified polyvinyl chloride is made by the following method:
By the polyvinyl chloride of 100 weight parts and 20 parts by weight of powder styrene-butadiene rubber(SBR) are blended forms;
By the polyvinyl chloride of 100 weight parts and 20 weight part paracril powder are blended forms;
The polyvinyl chloride of 100 weight parts and 20 weight part penta benzene rubber powder (i.e. the present invention) end are blendedly formed.
Table 1 modified polyvinyl chloride performance index
As can be seen from Table 1, utilize the performance of the polyvinyl chloride after powder penta benzene modified rubber more excellent, the polyvinyl chloride (PVC) of relatively traditional powder styrene butadiene rubber, the modification of paracril powder has stronger shock resistance, tensile property and breaking tenacity.Powder penta benzene rubber can be applied to the toughening modifying in the various goods such as PVC sheet, sheet material, tubing and profiled material, also can substitute powder butylbenzene and powdered nitrile rubber is applied to polyolefine, resol, the numerous areas such as cement, pitch.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. powder penta benzene rubber, is characterized in that, is made primarily of following component:
Described comonomer at least comprises isoprene and vinylbenzene, and described isoprene and described cinnamic weight ratio are 2:1 ~ 5:1;
Described grafted monomer comprises vinylbenzene and vinyl cyanide, and the weight ratio of described vinylbenzene and described vinyl cyanide is 3:2 ~ 2:3;
Described initiator comprise in Potassium Persulphate, Sodium Persulfate, ammonium persulphate one or more, described emulsifying agent comprised sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, one or more in sodium laurylsulfonate.
2. powder penta benzene rubber according to claim 1, it is characterized in that, described comonomer also comprises: vinyl monomer, and/or unsaturated fatty acids alkyl esters monomer, the consumption of described vinyl monomer and described unsaturated fatty acids alkyl esters monomer accounts for less than 20% of described comonomer gross weight.
3. powder penta benzene rubber according to claim 2, is characterized in that, described vinyl monomer comprise in divinyl, vinyl toluene, ethyl styrene one or more.
4. powder penta benzene rubber according to claim 2, it is characterized in that, described unsaturated fatty acids alkyl esters monomer comprise in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl methyl acrylate, ETHYL HEXYL ACRYLATE, butyl methacrylate one or more.
5. a preparation method for powder penta benzene rubber according to claim 1, is characterized in that, comprise the following steps:
A) water, comonomer, initiator, emulsifying agent are joined in reactor and be mixed to form polymeric solution, described polymeric solution reacts 10 ~ 15 hours under 50 ~ 70 DEG C of conditions, obtain latex, the consumption of described water is 1.2 ~ 1.5 times of described comonomer weight, the consumption of described initiator is 0.4 ~ 0.6% of described comonomer weight, and the consumption of described emulsifying agent is 1 ~ 2% of described comonomer weight;
B) described latex, grafted monomer and remaining water, remaining initiator, remaining emulsifying agent are mixed in reactor and form graft copolymer solution, described graft copolymer solution reacts 2 ~ 4 hours under 50 ~ 70 DEG C of conditions, obtain graft emulsion, then spraying dry, to obtain final product.
6. the preparation method of powder penta benzene rubber according to claim 5, it is characterized in that, steps A) in, when described mixing, also add ionogen, described ionogen comprises phosphoric acid salt, described electrolytical weight is 0.3 ~ 0.8% of described comonomer weight, preferably, described phosphoric acid salt comprises potassiumphosphate, and/or sodium phosphate.
7. the preparation method of powder penta benzene rubber according to claim 5, it is characterized in that, step B) in, after obtaining graft emulsion, before spraying dry, also comprise: in described graft emulsion, add weighting agent, and/or antioxidant, the weight of described weighting agent is 10 ~ 20% of the weight sum of described grafted monomer and described comonomer, and the total amount of described antioxidant is 0.4 ~ 0.6% of the weight sum of described grafted monomer and described comonomer.
8. the preparation method of powder penta benzene rubber according to claim 7, it is characterized in that, described weighting agent comprises titanium dioxide and/or calcium carbonate; Described antioxidant comprise in antioxidant 1076, antioxidant 2246, oxidation inhibitor 4720 one or more.
9. the preparation method of powder penta benzene rubber according to claim 5, it is characterized in that, step B) in, after obtaining graft emulsion, before spraying dry, also comprise: in described graft emulsion, add dispersion agent, described dispersion agent to comprise in styrene-maleic anhydride copolymer, polyvinyl alcohol, gelatin, Walocel MT 20.000PV, calcium stearate, lead stearate, Zinic stearas one or more, and the consumption of described dispersion agent is 3 ~ 5% of the weight of described grafted monomer.
10. the preparation method of powder penta benzene rubber according to claim 5, is characterized in that, described step B) in, described spray-dired temperature in is 130 ~ 140 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511030221.4A CN105384878B (en) | 2015-12-31 | 2015-12-31 | Penta benzene rubber of powder and preparation method thereof |
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| CN201511030221.4A CN105384878B (en) | 2015-12-31 | 2015-12-31 | Penta benzene rubber of powder and preparation method thereof |
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| CN105384878A true CN105384878A (en) | 2016-03-09 |
| CN105384878B CN105384878B (en) | 2018-05-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108976351A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | The preparation method of graft powder butadiene-styrene rubber |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3917748A (en) * | 1973-05-31 | 1975-11-04 | Standard Oil Co Ohio | Process for manufacture of rubber-modified copolymers of an olefinic nitrile and a vinyl aromatic monomer |
| JP2002294017A (en) * | 2001-03-30 | 2002-10-09 | Nippon A & L Kk | Compatible agent for recycling, method for recycling by using the same, recycled resin composition and sheet state molded material |
| CN1673262A (en) * | 2004-03-24 | 2005-09-28 | 中国石油天然气股份有限公司 | Powdered high styrene rubber and its prepn process |
| CN102417674A (en) * | 2011-09-15 | 2012-04-18 | 山东舜天力塑胶有限公司 | Polyvinyl chloride highly impact-resistant modifier and preparation method thereof |
| CN102863726A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | Synthetic method of PVC modifier |
| CN102924840A (en) * | 2012-10-09 | 2013-02-13 | 大连理工大学 | Method for preparing ABS resin from phenylethylene-butadiene-isoprene terpolymer composite latex by emulsion grafting |
| CN103539899A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of weather-resistant anti-aging ABS (acrylonitrile-butadiene-styrene) resin |
-
2015
- 2015-12-31 CN CN201511030221.4A patent/CN105384878B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3917748A (en) * | 1973-05-31 | 1975-11-04 | Standard Oil Co Ohio | Process for manufacture of rubber-modified copolymers of an olefinic nitrile and a vinyl aromatic monomer |
| JP2002294017A (en) * | 2001-03-30 | 2002-10-09 | Nippon A & L Kk | Compatible agent for recycling, method for recycling by using the same, recycled resin composition and sheet state molded material |
| CN1673262A (en) * | 2004-03-24 | 2005-09-28 | 中国石油天然气股份有限公司 | Powdered high styrene rubber and its prepn process |
| CN102863726A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | Synthetic method of PVC modifier |
| CN102417674A (en) * | 2011-09-15 | 2012-04-18 | 山东舜天力塑胶有限公司 | Polyvinyl chloride highly impact-resistant modifier and preparation method thereof |
| CN103539899A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of weather-resistant anti-aging ABS (acrylonitrile-butadiene-styrene) resin |
| CN102924840A (en) * | 2012-10-09 | 2013-02-13 | 大连理工大学 | Method for preparing ABS resin from phenylethylene-butadiene-isoprene terpolymer composite latex by emulsion grafting |
Non-Patent Citations (1)
| Title |
|---|
| 李薇: "一种特种丁腈橡胶的制备及工业放大", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976351A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | The preparation method of graft powder butadiene-styrene rubber |
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