CN105384878B - Penta benzene rubber of powder and preparation method thereof - Google Patents
Penta benzene rubber of powder and preparation method thereof Download PDFInfo
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- CN105384878B CN105384878B CN201511030221.4A CN201511030221A CN105384878B CN 105384878 B CN105384878 B CN 105384878B CN 201511030221 A CN201511030221 A CN 201511030221A CN 105384878 B CN105384878 B CN 105384878B
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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
- C08L2203/18—Applications used for pipes
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Abstract
A kind of penta benzene rubber of powder, is mainly made by following components：Comonomer 27~36%, grafted monomers 9~18%, initiator 0.18~0.23%, emulsifying agent 0.4~0.68%, water surplus.Wherein, comonomer includes at least isoprene and styrene, and grafted monomers include styrene and acrylonitrile.Polyvinyl chloride can improve shock resistance, tensile property by penta benzene modified rubber of powder.Moreover, it relates to the production method of the penta benzene rubber of powder.Production method has the characteristics that technique is simple, production efficiency is high.
Description
Technical field
The present invention relates to rubber production field, in particular to a kind of penta benzene rubber of powder and preparation method thereof.
Background technology
With the continuous improvement of scientific and technological level, the application field for expanding synthetic rubber is also increasingly subject to people's
Pay attention to.Simultaneously, also gradually risen using the exploitation and application study of rubber-modified plastics, modified cement, modified pitch etc..
But due to rubber cohesive force in itself and high resiliency, it is difficult to uniformly mix with the said goods, so not reaching modified expection
Effect.It is troublesome in poeration, labor intensity is big etc. in addition, also need stripping and slicing in process in itself there is niggerhead, be kneaded
Problem, liquid rubber and powdered rubber so last century early seventies developed countries begin one's study, gradually forms thereafter
Industrialized production.
Powdered rubber has many advantages, such as compared with niggerhead, for example, with the plastics, cement, pitch that are modified etc. easily
It is uniformly mixed, modified effect is good.Adhesive process is cut in addition, can cancel using powdered rubber, shortens mixing cycle, reduces energy consumption,
Reduce labor intensity.By being blended into powdered rubber masterbatch with other carbon blacks, fleut, rubber etc. can be directly processed into
Deng.
From the seventies later stage, the synthetic rubber and Polymer Processing of the developed country such as the U.S., Germany, Britain, Japan are looked forward to
Industry is all being directed to the research, development and production of rubber powder.What wherein production was most is powdered nitrile rubber, secondly powder fourth
Benzene, is mainly used for modified plastics and cement, pitch etc..Can be as the powder of modified additive in relation to preparation there is presently no seeing
The relevant report of penta benzene rubber.
The content of the invention
The first object of the present invention is to provide a kind of penta benzene rubber of powder, it is with more preferable mechanical performance.
The second object of the present invention is to provide a kind of preparation method of penta benzene rubber of powder, it is with technological process letter
Singly, the advantages that production efficiency is high.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of penta benzene rubber of powder, is mainly made by following components：By weight,
The comonomer includes at least isoprene and styrene, the weight ratio of the isoprene and the styrene
For 2:1~5:1；
The grafted monomers include styrene and acrylonitrile, and the weight ratio of the styrene and the acrylonitrile is 3:2~
2:3；
The initiator includes the one or more in potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, and the emulsifying agent includes
Cross lauryl sodium sulfate, neopelex, the one or more in dodecyl sodium sulfate.
The penta benzene rubber of powder is to be made using isoprene and styrene as main chain, using styrene and acrylonitrile as side chain
The graft copolymer of formation.Grafting processing reduces the melt viscosity of obtained penta benzene rubber of powder, improves its mobility, favorably
In to penta benzene rubber of powder progress secondary operation.In addition, grafting after penta benzene rubber of powder activation point it is more, be more conducive to and its
The components such as his rubber, plastics interact, so as to form the polymer of high molecular weight under the conditions of relatively mild, with
Improve the performance of the products such as rubber, plastics.The presence of side chain makes the spatial arrangement of the molecule segment of penta benzene rubber of powder more step up
Close, its is smaller, can reduce the particle diameter of product, easy to be mixed with other materials.
Persulfate has higher solubility in water, can produce the over cure acid ion with strong oxidation.Cross
Sulfate ion is hankered generating free radicals initiated polymerization in aqueous systems.Persulfate initiator is suitable for drawing under cryogenic conditions
Emulsion polymerization is sent out, can be to avoid due to emulsion polymerization temperature excessive the problem of causing reaction system stability poor.High temperature is anti-
The emulsion particle Brownian movement in reaction system should can be caused to aggravate, so that latex particle mutually collides polymerization, cause reactant
System stablizes decline.In addition, pyroreaction easily leads to monomer implode, and then the problems such as occurrence of equipment damage, loss of product.It is above-mentioned
The emulsifying agent of dodecane base system is anion surface active component, it has preferable solubility, to comonomer, connects in water
Branch monomer emulsification it is strong, comonomer, grafted monomers can be promoted fully to be scattered in aqueous systems, beneficial to obtain particle diameter compared with
Small penta benzene rubber of powder.
Above-mentioned penta benzene rubber appearance of powder is white powder, and apparent density is in 0.4g/cm3More than, 1000 μm of residue on sieves
Content is below 1%.After the degree of polymerization of 100 parts by weight is 1,000 penta benzene blend rubber of polyvinyl chloride and 20 parts by weight of powder,
Tensile strength is in more than 17MPa, and impact strength is in 9KJ/m2More than, fracture strength is in more than 17MPa, and elongation is 250%
More than.
Preferably, the comonomer further includes：Vinyl monomer, and/or unrighted acid alkyl esters monomer,
The dosage of the vinyl monomer and the unrighted acid alkyl esters monomer accounts for the comonomer gross weight
Less than 20%.
Vinyl monomer and the full, addition of fatty acid alkyl esters monomer, can improve product after comonomer polymerization
Activated centre quantity, more fully to polymerize with grafted monomers.
Preferably, the vinyl monomer includes butadiene, methyl styrene, one kind in ethyl styrene or more
Kind.
Vinyl monomer can provide vinyl for penta benzene rubber of powder, so as to improve penta benzene rubber of powder and have vinyl
Material between intermiscibility, and then reduce modified product manufacture difficulty.
Preferably, the unrighted acid alkyl esters monomer include methyl methacrylate, ethyl methacrylate,
Butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methyl acrylate, ethylacrylic acid oneself
One or more in ester, butyl methacrylate.
Unsaturated fat acid alkyl ester has plasticization, can reduce melt viscosity and the flowing of obtained penta benzene rubber of powder
Temperature, easy to carry out secondary operation to penta benzene rubber of powder.The unrighted acid of esterified with alkyl, acidity reduce, the elevation of boiling point
Without volatile, make polymerization process controllability higher.
The preparation method of above-mentioned penta benzene rubber of powder, comprises the following steps：
A) water, comonomer, initiator, emulsifying agent are added in reaction kettle and are mixed to form polymeric solution, the polymerization
Solution obtains latex, the dosage of the water is the comonomer weight when reaction 10~15 is small under the conditions of 50~70 DEG C
1.2~1.5 times, the dosage of the initiator is the 0.4~0.6% of the comonomer weight, and the dosage of the emulsifying agent is
The 1~2% of the comonomer weight；
B the latex, grafted monomers and remaining water, remaining initiator, remaining emulsifying agent) are mixed in reaction kettle
Interior formation grafting solution, the grafting solution obtain graft emulsion, then spray when reaction 2~4 is small under the conditions of 50~70 DEG C
It is dry, to obtain the final product.
First, the copolymer of isoprene and styrene is obtained by such as emulsion polymerization, then, using the copolymer as main chain
Graft polymerizing styrene and acrylonitrile side chain are carried out, so as to prepare graft copolymer.The preparation method passes through two polymerisations
Step, re-dry can obtain powdered rubber.Emulsion polymerization system easy heat radiation, avoids heat accumulation in polymerization process, so that
Reduce there is a situation where implode, while reduce the difficulty of thermal control.The viscosity of emulsion polymerization systems is low, mobility is high, is more conducive to
Made.Aqueous based systems so that polymerization process is safe and reliable.Spray drying is by the way that liquid material is sprayed at a high speed, drying,
Powder-product can be obtained, its is efficient, easy to operate.Since in drying process, rubber molecule does not bear larger shearing
Effect, the integrity degree of its strand are high, it is easier to are kneaded with other modified materials.
Preferably, step A) in, in the mixing, electrolyte is additionally added, the electrolyte includes phosphate, the electricity
The weight for solving matter is the 0.3~0.8% of the comonomer weight.
Electrolyte is prevented from contacting with each other between the copolymer in reaction system, bonded, and can reduce the sticky of reaction system
Degree, improve mobility, to be stirred mixing to reaction solution, makes polymerisation more abundant.
Preferably, the phosphate includes potassium phosphate, and/or sodium phosphate.
Preferably, step B) in, after obtaining graft emulsion, before spray drying, further include：Into the graft emulsion
Add filler, and/or antioxidant, the weight of the filler for the weight of the grafted monomers and the comonomer it
The 10~20% of sum, the total amount of the antioxidant for the sum of the weight of the grafted monomers and the comonomer 0.4~
0.6%.
Filler and antioxidant can be used as improving the performance of final products.Wherein, filler can reduce manufacturing process
In drying difficulty, improve rate of drying；Antioxidant can then improve the antioxygenic property of obtained powdered rubber, delay powder rubber
The ager process of glue, improves service life.
Preferably, the filler includes titanium dioxide, and/or calcium carbonate；The antioxidant includes antioxidant 1076, resists
One or more in oxidant 2246, antioxidant 4720.
Preferably, the calcium carbonate is precipitated calcium carbonate.
Preferably, step B) in, after obtaining graft emulsion, before spray drying, further include：Into the graft emulsion
Add dispersant, the dispersant includes styrene-maleic anhydride copolymer, polyvinyl alcohol, gelatin, hydroxymethyl cellulose, hard
One or more in resin acid calcium, lead stearate, zinc stearate, the dosage of the dispersant is the 3 of the weight of the grafted monomers
~5%.
Dispersant can prevent the mutual adhesion of polymer particle, the particle diameter of powdered rubber made from reduction.Styrene-
Copolymer-maleic anhydride, polyvinyl alcohol, gelatin, hydroxymethyl cellulose can avoid graft polymers mutually viscous in the reaction system
Knot, so as to lower the viscosity of reaction system, solution is more easy to disperse, and improves drying property, is more likely formed powdery.It is calcium stearate, hard
Resin acid lead, zinc stearate then have lubricating action, reduce the rubbing action between rubber particles after being grafted, and make the stream of reaction system
Dynamic property improves, it is easier to conveys and scattered.
Preferably, the inlet temperature of the spray drying is 130~140 DEG C.
Dry at such a temperature, the moisture rapid evaporation in solution can be made, reduce drying time, avoid powdered rubber from being heated
Time is too long or temperature is excessive and the problem of producing aging.
Beneficial effects of the present invention：Penta benzene rubber of powder provided by the invention can be used as modified additive to rubber, plastics, drip
The materials such as green grass or young crops are modified, and have preferable toughening effect.Penta benzene rubber of powder has preferable mobility, is storing and is transporting
During be not susceptible to lump, and transported using pipeline, therefore, the use of penta benzene rubber of powdered can improve modification
The automation of production and production efficiency.Intermiscibility between penta benzene rubber of collateralization and modified material is high, can reduce by penta
Mixing difficulty between benzene rubber and modified material.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer, is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
Present embodiments provide a kind of penta benzene rubber of powder, including following components：
800 grams of comonomer；200 grams of grafted monomers；4 grams of initiator；10 grams of emulsifying agent；1200 grams of water.
Wherein, comonomer includes isoprene and styrene, and the weight ratio of isoprene and styrene is 4:1；Grafting
Monomer includes styrene and acrylonitrile, and the weight ratio of styrene and acrylonitrile is 3:2；Initiator includes potassium peroxydisulfate, emulsifying agent
Including crossing lauryl sodium sulfate.
Above-mentioned penta benzene rubber of powder is made by the following method：
Step 1, by 960 grams of water, 800 grams of comonomers, 3.2 grams of initiators, 8 grams of emulsifying agents be added in reaction kettle and mix
Polymeric solution is formed, polymeric solution obtains latex when reaction 10 is small under the conditions of 50 DEG C；
Step 2, by latex, 240 grams of water, 200 grams of grafted monomers, 0.8 gram of initiator, 2 grams of emulsifying agents be mixed in reaction kettle
Interior formation grafting solution, grafting solution obtain graft emulsion, then dry, when reaction 2 is small under the conditions of 50 DEG C to obtain the final product.
Embodiment 2
Present embodiments provide a kind of penta benzene rubber of powder, including following components：
600 grams of comonomer；400 grams of grafted monomers；4 grams of initiator；10 grams of emulsifying agent；1200 grams of water.
Wherein, comonomer includes isoprene and styrene, and the weight ratio of isoprene and styrene is 5:1；Grafting
Monomer includes styrene and acrylonitrile, and the weight ratio of styrene and acrylonitrile is 2:3；Initiator includes sodium peroxydisulfate, emulsifying agent
Including crossing neopelex.
Above-mentioned penta benzene rubber of powder is made by the following method：
Step 1, by 720 grams of water, 600 grams of comonomers, 2.4 grams of initiators, 6 grams of emulsifying agents be added in reaction kettle and mix
Polymeric solution is formed, polymeric solution obtains latex when reaction 12 is small under the conditions of 65 DEG C；
Step 2, by latex, 480 grams of water, 400 grams of grafted monomers, 1.6 grams of initiators, 4 grams of emulsifying agents be mixed in reaction kettle
Interior formation grafting solution, grafting solution obtain graft emulsion, then dry, when reaction 2 is small under the conditions of 60 DEG C to obtain the final product.
Embodiment 3
Present embodiments provide a kind of penta benzene rubber of powder, including following components：
700 grams of comonomer；300 grams of grafted monomers；6 grams of initiator；20 grams of emulsifying agent；1560 grams of water.
Wherein, comonomer includes isoprene and styrene, and the weight ratio of isoprene and styrene is 9:2；Grafting
Monomer includes styrene and acrylonitrile, and the weight ratio of styrene and acrylonitrile is 1:1；Initiator includes ammonium persulfate, emulsifying agent
Including crossing dodecyl sodium sulfate.
Above-mentioned penta benzene rubber of powder is made by the following method：
1050 grams of water, 700 grams of comonomers, 4.2 grams of initiators, 14 grams of emulsifying agents, be added in reaction kettle and mix by step 1
Conjunction forms polymeric solution, and polymeric solution obtains latex when reaction 15 is small under the conditions of 70 DEG C；
Step 2, by latex, 510 grams of water, 300 grams of grafted monomers, 1.8 grams of initiators, 6 grams of emulsifying agents be mixed in reaction kettle
Interior formation grafting solution, grafting solution obtain graft emulsion, then dry, when reaction 4 is small under the conditions of 70 DEG C to obtain the final product.
Embodiment 4
Present embodiments provide a kind of penta benzene rubber of powder, including following components：
750 grams of comonomer；260 grams of grafted monomers；5.3 grams of initiator；14 grams of emulsifying agent；1339 grams of water.
Wherein, comonomer includes isoprene and styrene, and the weight ratio of isoprene and styrene is 21:5；Grafting
Monomer includes styrene and acrylonitrile, and the weight ratio of styrene and acrylonitrile is 6:5；Initiator includes ammonium persulfate, emulsifying agent
Including crossing dodecyl sodium sulfate.
Above-mentioned penta benzene rubber of powder is made by the following method：
Water, 750 grams of comonomers, 3.8 grams of initiators, 9.8 grams of emulsifying agents are added in reaction kettle and mixed by step 1,975
Polymeric solution is formed, polymeric solution obtains latex when reaction 13 is small under the conditions of 54 DEG C；
Step 2, by latex, 364 grams of water, 260 grams of grafted monomers, 1.5 grams of initiators, 4.2 grams of emulsifying agents be mixed in reaction
Grafting solution is formed in kettle, grafting solution obtains graft emulsion, then dry, when reaction 3 is small under the conditions of 67 DEG C to obtain the final product.
Embodiment 5
Present embodiments provide a kind of penta benzene rubber of powder, including following components：
530 grams of comonomer；243 grams of grafted monomers；3.7 grams of initiator；11.7 grams of emulsifying agent；785 grams of water；Potassium phosphate
2.5 gram；77.3 gram calcium carbonate；3 grams of antioxidant 1076s；4.6 grams of styrene-maleic anhydride copolymer.
Wherein, comonomer includes isoprene, styrene and butyl acrylate, isoprene, styrene and propylene
The weight ratio of acid butyl ester is 65:25:10；Grafted monomers include styrene and acrylonitrile, and the weight ratio of styrene and acrylonitrile is
3:2；Initiator includes ammonium persulfate, and emulsifying agent included dodecyl sodium sulfate.
Above-mentioned penta benzene rubber of powder is made by the following method：
Step 1, by 742 grams of water, 530 comonomers, 3 grams of initiators, 9 grams of emulsifying agents, 2.5 grams of potassium phosphates be added to reaction
Polymeric solution is mixed to form in kettle, polymeric solution obtains latex when reaction 13 is small under the conditions of 54 DEG C；
Step 2, by latex, 243 grams of water, 152 grams of grafted monomers, 0.7 gram of initiator, 2.7 grams of emulsifying agents, 4.6 grams of benzene second
Alkene-copolymer-maleic anhydride, which is mixed in reaction kettle, forms grafting solution, and grafting solution is obtained when reaction 3 is small under the conditions of 67 DEG C
Mix with calcium carbonate and antioxidant 1706 to graft emulsion, be then dried by spray drying tower again, spray drying
Inlet temperature is 130 DEG C, to obtain the final product.Styrene-maleic anhydride copolymer number-average molecular weight used in the present embodiment is 5000.
Embodiment 6
Present embodiments provide a kind of penta benzene rubber of powder, including following components：
500 grams of comonomer；227 grams of grafted monomers；Trigger 3.9 grams；13.3 grams of emulsifying agent；1013 grams of water；Sodium phosphate 4
Gram；154 grams of precipitated calcium carbonate；4.4 grams of antioxidant 2246s；11.4 grams of styrene-maleic anhydride copolymer.
Wherein, comonomer includes isoprene, styrene and butadiene, isoprene, styrene and butadiene
Weight ratio is 65:25:10；Grafted monomers include styrene and acrylonitrile, and the weight ratio of styrene and acrylonitrile is 3:2；Trigger
Agent includes sodium peroxydisulfate, and emulsifying agent included lauryl sodium sulfate.
Above-mentioned penta benzene rubber of powder is made by the following method：
650 grams of water, 500 grams of comonomers, 2.9 grams of initiators, 9 grams of emulsifying agents, 4 grams of sodium phosphates, be added to instead by step 1
Answer and polymeric solution is mixed to form in kettle, polymeric solution obtains latex when reaction 13 is small under the conditions of 54 DEG C；
Step 2, by latex, 363 grams of water, 227 grams of grafted monomers, 1 gram of initiator, 4.3 grams of emulsifying agents, 11.4 grams of benzene second
Alkene-copolymer-maleic anhydride, which is mixed in reaction kettle, forms grafting solution, and grafting solution is obtained when reaction 3 is small under the conditions of 67 DEG C
Mix with precipitated calcium carbonate and antioxidant 2246 to graft emulsion, be then dried by spray drying tower again, spraying is dry
Dry inlet temperature is 140 DEG C, to obtain the final product.The molecular weight of styrene-maleic anhydride copolymer is 6000 in the present embodiment.
Embodiment 7
Present embodiments provide a kind of penta benzene rubber of powder, including following components：
630 grams of comonomer；340 grams of grafted monomers；4.8 grams of initiator；12.6 grams of emulsifying agent；1479 grams of water；Sodium phosphate
3.8 gram；155 grams of titanium dioxide；4.9 grams of antioxidant 2246s；13.6 grams of hydroxymethyl cellulose.
Wherein, comonomer includes isoprene, styrene and butadiene, isoprene, styrene and butadiene
Weight ratio is 65:25:10；Grafted monomers include styrene and acrylonitrile, and the weight ratio of styrene and acrylonitrile is 3:2；Trigger
Agent includes sodium peroxydisulfate, and emulsifying agent included lauryl sodium sulfate.
Above-mentioned penta benzene rubber of powder is made by the following method：
Step 1, add 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
Polymeric solution is mixed to form in reaction kettle, polymeric solution obtains latex when reaction 13 is small under the conditions of 63 DEG C；
Step 2, by latex, 578 grams of water, 340 grams of grafted monomers, 1.6 grams of initiators, 4.4 grams of emulsifying agents, 13.6 grams of hydroxyl first
Base cellulose, which is mixed in reaction kettle, forms grafting solution, and grafting solution obtains grafting breast when reaction 3.5 is small under the conditions of 55 DEG C
Liquid is mixed with titanium dioxide and antioxidant 2246 again, is then dried by spray drying tower, the inlet temperature of spray drying
For 137 DEG C, to obtain the final product.
Test example 1
By the powder styrene butadiene rubber of in the market, powder nitrile rubber and the embodiment of the present invention 1 to (the numbering 1-7 of embodiment 7
Respectively correspond embodiment 1 to 7) provide penta benzene rubber of powder be used for modified polyvinyl chloride (degree of polymerization 1000), modification
The results are shown in Table 1, and wherein powder styrene butadiene rubber purchase is from Shandong Sheng Ya Chemical Co., Ltd.s, product identification
33010245016；Powder nitrile rubber is bought from Shandong Sheng Ya Chemical Co., Ltd.s, product type PNBR-01.Modified side
Method following article.
Modified polyvinyl chloride is made by the following method：
The polyvinyl chloride of 100 parts by weight and the blending of 20 parts by weight of powder butadiene-styrene rubber are formed；
The polyvinyl chloride of 100 parts by weight and the blending of 20 parts by weight nitrile rubber powder are formed；
The polyvinyl chloride of 100 parts by weight and 20 parts by weight, penta benzene rubber powder (i.e. of the invention) end blending are formed.
1 modified polyvinyl chloride performance indicator of table
As can be seen from Table 1, the performance using the polyvinyl chloride after penta benzene modified rubber of powder is more excellent, relatively traditional
Powder styrene butadiene rubber, nitrile rubber powder be modified polyvinyl chloride (PVC) have stronger shock resistance, tensile property and
Fracture strength.The toughness reinforcing that penta benzene rubber of powder can be applied in the various products such as PVC sheet, plate, tubing and profile shapes changes
Property, powder butylbenzene can also be substituted and powdered nitrile rubber is applied to polyolefin, the numerous areas such as phenolic resin, cement, pitch.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for the skill of this area
For art personnel, the invention may be variously modified and varied.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. penta benzene rubber of powder, it is characterised in that be mainly made by following components：
The comonomer includes at least isoprene and styrene, and the weight ratio of the isoprene and the styrene is 2:
1~5:1；
The grafted monomers include styrene and acrylonitrile, and the weight ratio of the styrene and the acrylonitrile is 3:2~2:3；
The initiator includes the one or more in potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, and the emulsifying agent included ten
Sodium dialkyl sulfate, neopelex, the one or more in dodecyl sodium sulfate；
The bulk density of the penta benzene rubber of powder is in 0.4g/cm3More than, the content of 1000 μm of residue on sieves is described below 1%
Penta benzene rubber of powder is made by the following method：
After mixing the water of the comonomer, the initiator of partial amount, the emulsifying agent of partial amount and partial amount,
Carry out polymerisation and form latex；
By the latex and the grafted monomers, the initiator of surplus, the emulsifying agent of surplus and surplus
Water mixing after, carry out polymerisation formed graft emulsion；And
The graft emulsion is spray-dried, the inlet temperature of the spray drying is 130~140 DEG C.
2. penta benzene rubber of powder according to claim 1, it is characterised in that the comonomer further includes：It is vinyl-based
Monomer, and/or unrighted acid alkyl esters monomer, the vinyl monomer and the unrighted acid alkyl esters
The dosage of monomer accounts for less than the 20% of the comonomer gross weight.
3. penta benzene rubber of powder according to claim 2, it is characterised in that the comonomer further includes butadiene, first
One or more in base styrene, ethyl styrene.
4. penta benzene rubber of powder according to claim 2, it is characterised in that the unrighted acid alkyl esters monomer
Including methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid
One or more in butyl ester, ethyl methyl acrylate, ETHYL HEXYL ACRYLATE, butyl methacrylate.
5. the preparation method of the penta benzene rubber of powder described in a kind of claim 1, it is characterised in that comprise the following steps：
A) water, comonomer, initiator, emulsifying agent are added in reaction kettle and are mixed to form polymeric solution, the polymeric solution
When reaction 10~15 is small under the conditions of 50~70 DEG C, obtain latex, the dosage of the water be the comonomer weight 1.2~
1.5 times, the dosage of the initiator is the 0.4~0.6% of the comonomer weight, and the dosage of the emulsifying agent is described common
The 1~2% of polycondensation monomer weight；
B the latex, grafted monomers and remaining water, remaining initiator, remaining emulsifying agent) are mixed in shape in reaction kettle
Into grafting solution, the grafting solution obtains graft emulsion when reaction 2~4 is small under the conditions of 50~70 DEG C, and then spraying is dry
Dry, to obtain the final product, the inlet temperature of the spray drying is 130~140 DEG C.
6. the preparation method of penta benzene rubber of powder according to claim 5, it is characterised in that step A) in, described mixed
During conjunction, electrolyte is additionally added, the electrolyte includes phosphate, and the weight of the electrolyte is the comonomer weight
0.3~0.8%.
7. the preparation method of penta benzene rubber of powder according to claim 6, it is characterised in that the phosphate includes phosphoric acid
Potassium, and/or sodium phosphate.
8. the preparation method of penta benzene rubber of powder according to claim 5, it is characterised in that step B) in, it is grafted
After lotion, before spray drying, further include：Filler, and/or antioxidant are added into the graft emulsion, it is described to fill out
The weight for filling agent is the 10~20% of the sum of the weight of the grafted monomers and the comonomer, the total amount of the antioxidant
For the 0.4~0.6% of the sum of the weight of the grafted monomers and the comonomer.
9. the preparation method of penta benzene rubber of powder according to claim 8, it is characterised in that the filler includes titanium white
Powder and/or calcium carbonate；The antioxidant includes antioxidant 1076, antioxidant 2246, one kind in antioxidant 4720 or more
Kind.
10. the preparation method of penta benzene rubber of powder according to claim 5, it is characterised in that step B) in, it is grafted
After lotion, before spray drying, further include：Add dispersant into the graft emulsion, the dispersant include styrene-
In copolymer-maleic anhydride, polyvinyl alcohol, gelatin, hydroxymethyl cellulose, calcium stearate, lead stearate, zinc stearate it is a kind of or
A variety of, the dosage of the dispersant is the 3~5% of the weight of the grafted monomers.
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| CN1309776C (en) * | 2004-03-24 | 2007-04-11 | 中国石油天然气股份有限公司 | Powdered high styrene rubber and its prepn process |
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| CN102417674B (en) * | 2011-09-15 | 2013-04-24 | 山东舜天力塑胶有限公司 | Polyvinyl chloride highly impact-resistant modifier and preparation method thereof |
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Effective date of registration: 20190918 Address after: 337016 No. 3-188, Industrial Park D, Pingxiang City, Jiangxi Province Patentee after: Jiangxi Yuefeng Group Environmental Protection New Material Co., Ltd. Address before: 337000, Jinfeng Road, 21 West Development Zone, Pingxiang Economic Development Zone, Jiangxi, Pingxiang Patentee before: JIANGXI YUEFENG POLYMER CO., LTD. |