CN105273328A - Transparent cold-resistant polyvinylchloride modified material, and preparation method and application thereof - Google Patents
Transparent cold-resistant polyvinylchloride modified material, and preparation method and application thereof Download PDFInfo
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- CN105273328A CN105273328A CN201410290416.1A CN201410290416A CN105273328A CN 105273328 A CN105273328 A CN 105273328A CN 201410290416 A CN201410290416 A CN 201410290416A CN 105273328 A CN105273328 A CN 105273328A
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Abstract
The invention relates to a polyvinylchloride (PVC) modified material. Every unit of the material comprising 100 parts by weight of polyvinylchloride resin comprises, by weight, (A) 1-10 parts of quasi-styrene which is a graft copolymer of rubber or elastomer and alpha-methyl styrene, (B) 5-30 parts of thermoplastic polyurethane, (C) a thermal stabilizer, (D) a plasticizer and (E) an optional auxiliary plasticizer. According to the polyvinylchloride modified material, on a basis that good transparency of polyvinylchloride resin is substantially maintained, the plasticizing temperature is reduced and the cold resistance is improved, such that comprehensive performances of the material are improved. The invention also relates to a method for preparing the polyvinylchloride modified material. The method comprises the steps of melting and kneading all components of the polyvinylchloride modified material. The PVC modified material is transparent and environment-friendly. The plasticizing temperature is greatly reduced, and the material also has good cold resistance. Therefore, the material can be used for preparing transparent environment-friendly PVC soft products used under low-temperature environments.
Description
Technical field
The present invention relates to a kind of polyvinyl chloride modifying material, more specifically relate to a kind of transparent and to have the cold resistance polyvinyl chloride of lower plasticization temperature material modified, this material especially soft PVC is material modified.The invention still further relates to the Synthesis and applications of this polyvinyl chloride modifying material.
Technical background
Polyvinyl chloride (PVC) is a kind of general-purpose plastics of high comprehensive performance, is widely used in all trades and professions, is also the second largest resin variety being only second to polyethylene (PE) at present.PVC has the advantages such as oil resistant, acid and alkali-resistance, excellent electrical properties, light transmission be good.The soft product of PVC refer in formula, be added with softening agent and make there is certain flexible PVC product.Flexible PVC goods occupy critical role, are widely used in the aspects such as building and ornament materials, leatheroid, film, flexible pipe, cable, shoemaking.In recent years, PVC soft goods, in the application in the fields such as automobile, electronics, health care, also obtains development.
At present, flexible PVC material mainly uses phthalic ester plasticizer to carry out plasticising.Studies have found that, universal PVC plasticizer phthalic acid ester has potential carinogenicity, again due to the small molecules characteristic of itself, very easily moves and is extracted out by solvent, not only affecting product performance, also directly threaten the health of the mankind in PVC product.Many countries all take certain restriction one after another to the use of these conventional plasticizers, in the even total ban of some field.In order to overcome this shortcoming, main countermeasure adopts asepsis environment-protecting class softening agent to carry out plasticising to PVC.
In addition, ordinary soft PVC material is easily hardening at low temperatures, follows the string, thus loses use value.Blending and modifying improves the physicals of flexible PVC and the simple and direct of work-ing life and effective means.Use various different macromolecule modifier to carry out blending and modifying to flexible PVC, make the flexibility that flexible PVC remains certain within the scope of use temperature.
The open CN101177513A of Chinese patent application adopts polyvinyl chloride, the auxiliary agent of chloride graft acrylate and urethane and surplus has blendedly obtained low-temperature resistant flexile PVC modified material.The open CN12051007A of Chinese patent application adopts the powdered rubber with crosslinking structure to carry out modification to soft PVC, has obtained the soft PVC with outstanding temperature tolerance and higher tensile strength and elongation material modified.But the polyvinyl chloride modifying material mentioned in these two patent applications all can not ensure that PVC has the good transparency, and while raising winter hardiness, the object reducing plasticization temperature and environmental protection can not be reached.
Therefore, still need one not only to have good transparency, but also have lower plasticization temperature and cold-resistant polyvinyl chloride modifying material, especially soft PVC is material modified.
Summary of the invention
In view of above-mentioned condition of the prior art, the present inventor has carried out going deep into and studying widely in field of polyvinyl chloride material, to find a kind of transparent, there is lower plasticization temperature and cold-resistant polyvinyl chloride modifying material, especially soft PVC is material modified.Found that, thermoplastic polyurethane (TPU) and quasi-styrene are included in polyvinyl chloride (PVC) RESINS as properties-correcting agent, while the good transparency of basic maintenance polyvinyl chloride (PVC) RESINS own, can also reduce its plasticization temperature, improve its winter hardiness, thus improve its over-all properties.The present inventor completes the present invention based on aforementioned discovery just.
Therefore, an object of the present invention is to provide a kind of polyvinyl chloride modifying material, especially soft PVC is material modified.This material can ensure the transparency that PVC is good, asepsis environment-protecting, under the prerequisite that hardness does not significantly decline, improve the winter hardiness of PVC, and the plasticization temperature of PVC is reduced, significantly reduce the thermolysis degree in the PVC course of processing, improve the performance of PVC, widen the Application Areas of PVC.
Another object of the present invention is to provide a kind of method preparing polyvinyl chloride modifying material of the present invention.
Another object of the present invention is to provide polyvinyl chloride modifying material and is preparing polyvinyl chloride hose, the purposes especially in transparent polyvinyl chloride flexible pipe.
The technical scheme realizing above-mentioned purpose of the present invention can be summarized as follows:
1, a polyvinyl chloride modifying material, the polyvinyl chloride (PVC) RESINS often comprising resin based on 100 weight parts in this material just comprises following component:
A) 1-10 weight part, the quasi-styrene of preferred 2-6 weight part, it is the graft copolymer of rubber or elastomerics and alpha-methyl styrene;
B) 5-30 weight part, the thermoplastic polyurethane of preferred 10-25 weight part;
C) thermo-stabilizer, preferred 1-4 weight part, the more preferably thermo-stabilizer of 1.5-3.5 weight part;
D) softening agent, preferred 20-50 weight part, is more preferably the softening agent of 25-35 weight part; With
E) optional extender plasticizer, preferred 1-6 weight part, is more preferably the extender plasticizer of 2-5 weight part,
Wherein each number is the parts by weight that polyvinyl chloride modifying material often comprises each component that 100 weight part polyvinyl chloride (PVC) RESINS comprise.
2, the polyvinyl chloride modifying material as described in the 1st, the weight-average molecular weight of wherein said polyvinyl chloride (PVC) RESINS is 10-20 ten thousand, is preferably 12.5-15 ten thousand, especially for the trade mark of Tianjin organic chemical industry two factory is the polyvinyl chloride of SG3 and/or SG4.
3, the polyvinyl chloride modifying material as described in the 1st or 2, wherein said thermoplastic polyurethane is polyester type thermoplastic polyurethane.
4, the polyvinyl chloride modifying material according to any one of 1-3 item, wherein said thermoplastic polyurethane has the shore hardness of 60-70A; And/or the weight-average molecular weight of thermoplastic polyurethane is 200,000-28 ten thousand, be preferably 200,000-26 ten thousand.
5., as the polyvinyl chloride modifying material according to any one of 1-4 item, the rubber or the elastomerics that wherein form described quasi-styrene are selected from paracril, vinyl-vinyl acetate copolymer elastomerics, ethylene-propylene rubber(EPR) and cis-1,4-polybutadiene rubber.
6, the polyvinyl chloride modifying material according to any one of 1-5 item, the weight-average molecular weight of wherein said quasi-styrene is 6-18 ten thousand, is preferably 7-10 ten thousand.
7., as the polyvinyl chloride modifying material according to any one of 1-6 item, in wherein said quasi-styrene, the weight percentage of α-methylstyrenemonomer unit is 40%-80%, and the weight percentage of rubber or elastomeric monomers unit is 20%-60%; The weight percentage of preferred α-methylstyrenemonomer unit is 60%-80%, and the weight percentage of rubber or elastomeric monomers unit is 20%-40%; Particularly preferably described quasi-styrene is selected from the trade mark of wishing that synthetic materials factory produces in Qinyang, Henan is the quasi-styrene of C-10 and/or LE.
8, the polyvinyl chloride modifying material according to any one of 1-7 item, wherein said thermo-stabilizer be selected from lower group one or more: metal soap stablizer, liquid composite stabilizing agent and composition metal soap stablizer; Be preferably liquid composite stabilizing agent; Be more preferably the calcium-zinc composite stabilizing agent in liquid composite stabilizing agent.
9, the polyvinyl chloride modifying material according to any one of 1-8 item, wherein said softening agent be selected from lower group one or more: trimellitic acid three monooctyl ester (TOTM), tributyl citrate (TBC), tributyl acetylcitrate (ATBC), hexanaphthene-1,2-dioctyl phthalate diisononyl esters (DINCH) and hexanaphthene-1,2-dioctyl phthalate di-isooctyl (DEHCH); Preferred hexanaphthene-1,2-dioctyl phthalate diisononyl esters (DINCH).
10, the polyvinyl chloride modifying material according to any one of 1-9 item, wherein said auxiliary stabilizer is epoxy soybean oil (EOS).
11, prepare a method for the polyvinyl chloride modifying material according to any one of 1-10 item, comprise each component melts comprised by polyvinyl chloride modifying material and mediate; Preferably this melt kneading is carried out in twin screw extruder, this twin screw extruder has five sections of temperature control districts successively from opening for feed to discharge port, and every district temperature controls as follows: a district temperature 135-160 DEG C, two district temperature 135-155 DEG C, three district temperature 132-155 DEG C, four district temperature 130-150 DEG CHe five district temperature 130-148 DEG C.
12. if the polyvinyl chloride modifying material according to any one of 1-10 item is at manufacture polyvinyl chloride hose, the purposes especially in transparent polyvinyl chloride flexible pipe.
Embodiment
According to an aspect of the present invention, provide a kind of polyvinyl chloride modifying material, the polyvinyl chloride (PVC) RESINS often comprising resin based on 100 weight parts in this material just comprises following component:
A) 1-10 weight part quasi-styrene, it is the graft copolymer of rubber or elastomerics and alpha-methyl styrene;
B) thermoplastic polyurethane of 5-30 weight part;
C) thermo-stabilizer;
D) softening agent; With
E) optional extender plasticizer,
Wherein each number is the parts by weight that polyvinyl chloride modifying material often comprises each component that 100 weight part polyvinyl chloride (PVC) RESINS comprise.
Polyvinyl chloride modifying material of the present invention comprises resin based on polyvinyl chloride (PVC) RESINS, i.e. basal component.In the present invention, polyvinyl chloride resin can be chosen in wide region.In a preferred embodiment of the invention, the weight-average molecular weight of polyvinyl chloride (PVC) RESINS is 10-20 ten thousand, preferred 12.5-15 ten thousand.Advantageously, the heterogeneity index M of this polyvinyl chloride basis resin
w/ M
nbe generally 3-5, preferred 3.5-4.5.The present invention especially preferably uses the trade mark of Tianjin organic chemical industry two factory to be SG2, SG3, SG4 and/or SG5, the especially polyvinyl chloride (PVC) RESINS of SG3 and/or SG4.
In polyvinyl chloride modifying material of the present invention, often comprise the polyvinyl chloride resin of 100 weight parts, just comprise 5-30 weight part, the thermoplastic polyurethane (TPU) of preferred 10-25 weight part is as B component).The features such as TPU is a kind of novel Polyurethane Thermoplastic Elastomer, and TPU has higher mechanical property, good elasticity, wear-resisting, oil resistant, cold-resistant, radiation hardness, resistance to ozone, dielectric properties are good.Select TPU as the properties-correcting agent of PVC, effectively can improve the mechanical property, elastic performance etc. of blend.According to the difference of long chain diol type used in TPU building-up process, polyester type TPU and polyether-type TPU can be divided into.Preferred polyester type TPU of the present invention.By changing the proportioning of each reactive component of TPU, can obtain the product of different hardness, the preferred shore hardness of the present invention is the TPU of 60-70A, especially has the polyester type TPU of this hardness.
It will be understood by those skilled in the art that " thermoplastic polyurethane " makes vulcabond or polyisocyanates and at least one polymer diol compound react the polymkeric substance obtained for being described through.This vulcabond or polyisocyanates are defined as the isocyanic ester containing the isocyanate functional group of more than 2 or 2 in this article, the example comprises aliphatic series, alicyclic, araliphatic and aromatic isocyanate, preferably aliphatic series and cyclic aliphatic two or polyisocyanates, especially vulcabond.They are used alone or use with the mixture of two or more.
The example of suitable aliphatic vulcabond comprises the α with 5-20 carbon atom, ω-alkylene diisocyanate, such as 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethylammonium-hexamethylene diisocyanate, 2-methyl isophthalic acid, 5-pentamethylene diisocyanate etc.The aliphatic polyisocyanate having and be less than 5 carbon atoms can be used, but compare not too preferred, because they have high volatility and toxicity.Preferred aliphatic vulcabond comprises 1,6-hexamethylene diisocyanate, 2,2,4-trimethylammoniums-hexamethylene diisocyanate and 2,4,4-trimethylammonium-hexamethylene diisocyanate.
The example of suitable cycloaliphatic diisocyanates comprises dicyclohexyl methane diisocyanate, isophorone diisocyanate, Isosorbide-5-Nitrae-cyclohexyl diisocyanate, 1,3-Methylcyclohexyl diisocyanate etc.Preferred cycloaliphatic diisocyanates comprises dicyclohexyl methane diisocyanate and isophorone diisocyanate.
The example of suitable araliphatic vulcabond comprises a tetramethyl-m-xylylene diisocyanate, to tetramethylxylylene diisocyanate, Isosorbide-5-Nitrae-xylylene diisocyanate, 1,3-xylylene diisocyanate etc.Preferred araliphatic vulcabond is tetramethyl-m-xylylene diisocyanate.
The example of suitable aromatic diisocyanate comprises 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, naphthalene diisocyanate etc.Preferred aromatic diisocyanate is tolylene diisocyanate and 4,4 '-diphenylmethanediisocyanate.
As polymer diol, it is polyester glycol and/or polyether glycol especially.
The esterification products that polyester glycol is normally prepared by making the glycol of Dicarboxylic Acids or its acid anhydrides and stoichiometric excess react.Glycol for the preparation of polyester diol comprises: aklylene glycol, such as ethylene glycol, 1, 2-and 1, ammediol, 1, 2-butyleneglycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, hexylene glycol, neopentyl glycol, 1, 6-hexylene glycol, 1, 8-ethohexadiol, and other glycol, as dihydroxyphenyl propane, cyclohexane diol, cyclohexanedimethanol (1, the two methylol hexanaphthene of 4-), 2-methyl isophthalic acid, ammediol, 2, 2, 4-trimethylammonium-1, 3-pentanediol, glycol ether, triglycol, Tetraglycol 99, polyoxyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polytetramethylene glycol, dimerization glycol, hydroxylation bis-phenol, polyether glycol, the glycol etc. of halogenation, and their mixture.Preferred glycol comprises ethylene glycol, glycol ether, butyleneglycol, hexylene glycol and neopentyl glycol.Suitable carboxylic for the preparation of polyester glycol comprises di-carboxylic acid and acid anhydrides thereof, the isomer of such as toxilic acid, maleic anhydride, succsinic acid, pentanedioic acid, Pyroglutaric acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, (neighbour) phthalic acid, (neighbour) phthalic acid, (neighbour) phthalate anhydride, fumaric acid, dimer (fatty acid) yl are as oleic acid etc., and their mixture.Preferred di-carboxylic acid for the preparation of polyester glycol comprises aliphatic series or aromatic dicarboxylate.
The example of suitable polyester glycol comprises poly-(adipate diol ester), poly-(ethylene glycol terephthalate) dibasic alcohol, polycaprolactone diols, phthalic acid dibasic alcohol, sulfonation and phosphorated dibasic alcohol etc., and their mixture.
Preferred polyester glycol comprises poly-(tetramethylene adipate); Hexylene glycol hexanodioic acid isophthalic polyester, as hexane adipate isophthalic acid ester; Hexylene glycol neopentyl glycol adipate polyester glycol; And also have propylene glycol maleic anhydride adipate polyester glycol, such as hexylene glycol neopentyl glycol fumarate polyester glycol.
Polyether glycol by make initial compounds containing hydrogen atoms as water or about the glycol as described in preparation polyester diol and aklylene glycol or cyclic ethers as ethylene glycol, propylene glycol, butyleneglycol, vinylbenzene glycol, ethylene oxide, propylene oxide, 1, the reaction of 2-oxybutylene, 2,3-oxybutylenes, trimethylene oxide, tetrahydrofuran (THF), Epicholorohydrin etc. and their mixture obtains in a known way.Preferred polyethers comprises polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran and ethylene glycol/propylene glycol copolymers.Polyoxyethylene glycol and polypropylene glycol can use with itself or use with physical blending thing.When by propylene oxide and ethylene oxide copolymerization, these oxypropylene/oxyethylene copolymers can use as unregulated polymer or segmented copolymer.
As thermoplastic polyurethane used in the present invention, can mention that aliphatic diisocyanate (as HMDI), alicyclic diisocyanate (as IPDI) or aromatic diisocyanate are (as 4,4'-, 2,4'-and/or 2,2 '-diphenylmethanediisocyanate, or tolylene diisocyanate), the urethane formed with polymer diatomic alcohol.
For this thermoplastic polyurethane, it both by the currently known methods preparation in this area, also commercially can obtain, as the example of this thermoplastic polyurethane, can mention the TPU-1180A of BASF AG, TPU-S90A, B98A; The 345X of Beyer Co., Ltd, DP3685AU, DP3690AU, DP3695AU, DP3660DU etc.Advantageously, the weight-average molecular weight for thermoplastic polyurethane of the present invention is 200,000-28 ten thousand, is preferably 200,000-26 ten thousand.
In polyvinyl chloride modifying material of the present invention, often comprise the polyvinyl chloride resin of 100 weight parts, just comprise 1-10 weight part, the quasi-styrene of preferred 2-6 weight part is as component A).This quasi-styrene is the graft copolymer of rubber or elastomerics and alpha-methyl styrene, has thus had alpha-methyl styrene polymer and rubber or elastomeric performance characteristics concurrently, can improve the processing characteristics of PVC, improves the winter hardiness etc. of PVC.In the present invention, quasi-styrene does not have nucleocapsid structure, is non-nucleocapsid multipolymer.
In the present invention, can be paracril, vinyl-vinyl acetate copolymer elastomerics, ethylene-propylene rubber(EPR), cis-1,4-polybutadiene rubber etc. with the rubber of alpha-methyl styrene grafting or elastomerics.As the quasi-styrene properties-correcting agent for modification PVC material of the present invention, its weight-average molecular weight is generally 6-18 ten thousand, is preferably 7-10 ten thousand.
In a preferred embodiment of the invention, the weight percentage of the α-methylstyrenemonomer unit in quasi-styrene is 40%-80%, and the weight percentage of rubber or elastomeric monomers unit is 20%-60%; The weight percentage of preferred α-methylstyrenemonomer unit is 60%-80%, and the weight percentage of rubber or elastomeric monomers unit is 20%-40%.
In the present invention, quasi-styrene is known or prepares by methods known in the art.Such as, rubber or elastomerics and α-methylstyrenemonomer are carried out ionic entities polymerization using Lewis acid initiator system as initiator.
As the example of quasi-styrene of the present invention, can mention that the trade mark that Qinyang, Henan wishes that synthetic materials factory produces is the quasi-styrene of C-10 (central rubber is paracril) and LE (central elastomerics is vinyl-vinyl acetate copolymer elastomerics).
Usually thermo-stabilizer that conventional polyvinyl chloride material require comprises also is comprised as component C) in polyvinyl chloride modifying material of the present invention.Preferably, polyvinyl chloride modifying material of the present invention often comprises the polyvinyl chloride resin of 100 weight parts, just comprises the thermo-stabilizer of 1-4 weight part, the thermo-stabilizer of preferred 1.5-3 weight part.Thermo-stabilizer can catch the HCl with self-catalysis that polyvinyl chloride resin is released, or the unstable polyolefin structure that can produce with polyvinyl chloride resin plays addition reaction, to stop or to alleviate the decomposition of polyvinyl chloride resin.As thermo-stabilizer, any thermo-stabilizer being applicable to PVC material all can be used for the present invention.Preferred thermo-stabilizer be selected from lower group one or more: metal soap stablizer, liquid composite thermal stabilizer and composition metal soap stablizer.As the example of metal soap stablizer, can mention barium stearate, lauric acid every etc.As the example of liquid composite thermal stabilizer, liquid barium/chromium/zinc stabilizer, liquid calcium/zinc stabilizer etc. can be mentioned.As composition metal soap stablizer, calcium-zinc composite stabilizing agent and barium zinc composite stabilizer can be mentioned, such as calcium stearate/Zinic stearas one package stabilizer.In the present invention, the calcium-zinc composite stabilizing agent that especially preferred liquid is nontoxic.
Calcium-zinc composite stabilizing agent is the hot worked conventional stablizer of PVC material, and it can by by composite for one or more in calcium stearate and Zinic stearas and polyvalent alcohol, phosphorous acid ester, beta-diketon, zeolite and hydrotalcite and obtain.As polyvalent alcohol, such as, can mention ethylene glycol, 1,2-PD, BDO, neopentyl glycol, Diethylene Glycol, dipropylene glycol etc.As phosphorous acid ester, both solid phosphorous acid ester can be used, also can use liquid phosphite, triphenyl phosphite, phosphorous acid phenylbenzene one monooctyl ester, phosphorous acid phenylbenzene one ester in the last of the ten Heavenly stems, tricresyl phosphite (nonyl phenyl ester) etc. can be mentioned as the example.As beta-diketon, beta-diketon stearoyl benzoyl methane (molecular formula: C can be mentioned
26h
42o
2, molecular weight: 386.6).
Usually softening agent that conventional polyvinyl chloride material require comprises also is comprised as component D) in polyvinyl chloride modifying material of the present invention.Preferably, polyvinyl chloride modifying material of the present invention often comprises the polyvinyl chloride resin of 100 weight parts, just comprises the softening agent of 20-50 weight part, the softening agent of preferred 25-35 weight part.Softening agent can make its snappiness strengthen, and easily processes, and the addition difference of softening agent determines the hardness of goods.As softening agent, any softening agent being applicable to PVC material all can be used for the present invention.Preferred plasticizer is non-phthalate environment-friendly plasticizer.As non-phthalate environment-friendly plasticizer, trimellitic acid three monooctyl ester (TOTM), tributyl citrate (TBC), tributyl acetylcitrate (ATBC), hexanaphthene-1 can be mentioned, 2-dioctyl phthalate diisononyl esters (DINCH) and hexanaphthene-1,2-dioctyl phthalate di-isooctyl (DEHCH).Particularly preferably hexanaphthene-1,2-dioctyl phthalate diisononyl esters (DINCH) is as softening agent in the present invention, and this softening agent asepsis environment-protecting, plasticization effect is good.
Advantageously, the extender plasticizer that conventional polyvinyl chloride material require comprises can usually also be comprised in polyvinyl chloride modifying material of the present invention.Preferably, polyvinyl chloride modifying material of the present invention often comprises the polyvinyl chloride resin of 100 weight parts, just comprises the extender plasticizer of 1-6 weight part, the extender plasticizer of preferred 2-5 weight part.Extender plasticizer mainly plays the effect of auxiliary plasticising.The preferred epoxy soybean oil of the present invention (EOS) is as extender plasticizer.
For the purpose of the present invention, all weight-average molecular weight related to and number-average molecular weight are and are obtained by gel permeation chromatography measurement, except being otherwise noted.
In a particularly preferred embodiment of the present invention, the polyvinyl chloride basis resin that polyvinyl chloride modifying material of the present invention often comprises 100 weight parts just comprises following component:
A) quasi-styrene of 2-6 weight part;
B) thermoplastic polyurethane of 10-25 weight part;
C) thermo-stabilizer of 1.5-3 weight part;
D) softening agent of 25-35 weight part; With
E) extender plasticizer of 2-5 weight part,
Wherein each number is the parts by weight that polyvinyl chloride modifying material often comprises each component that 100 weight part polyvinyl chloride (PVC) RESINS comprise.
According to another aspect of the present invention, provide a kind of method preparing polyvinyl chloride modifying material of the present invention, the method comprises each component melts comprised by polyvinyl chloride modifying material and mediates.
Before melt kneading, advantageously, each component that polyvinyl chloride modifying material of the present invention comprises is mixed in a mixer.The equipment implementing melt kneading is conventional, can mention mill, Banbury mixer, single screw extrusion machine, twin screw extruder etc.The temperature of melt kneading is also conventional, as long as can by kneaded together for each component melts of PVC material of the present invention.Typically, melt kneading is carried out at the temperature of 140-195 DEG C.
In a preferred embodiment of the inventive method, the melt kneading of each component that polyvinyl chloride modifying material comprises is carried out in twin screw extruder, this twin screw extruder has five sections of temperature control districts successively from opening for feed to discharge port, and every district temperature controls as follows: a district temperature 135-160 DEG C, two district temperature 135-155 DEG C, three district temperature 132-155 DEG C, four district temperature 130-150 DEG CHe five district temperature 130-148 DEG C.
Polyvinyl chloride modifying material of the present invention is not only transparent, has lower plasticization temperature, cold-resistant, but also is a kind of polyvinyl chloride modifying material of environmental protection soft.
Therefore, according to last aspect of the present invention, provide polyvinyl chloride modifying material of the present invention at manufacture polyvinyl chloride hose, the purposes especially in transparent polyvinyl chloride flexible pipe.
The material modified not only environmentally-friendly transparent of PVC of the present invention, and while greatly reducing plasticization temperature, also there is good winter hardiness, therefore may be used for preparing the environmentally-friendly transparent PVC soft goods being applicable to low temperature environment.
Embodiment
By embodiment, the present invention is described in more detail below.These embodiments are all only to the description of the optimum embodiment of the present invention, do not have any restriction to scope of the present invention
In following each embodiment and comparative example, if be not particularly illustrated, each component concentration is weight fraction.
In following embodiment and comparative example, following methods is adopted to test gained polyvinyl chloride modifying material:
Transmittance and mist degree test: transmittance and the mist degree of testing sample by GB/T2410-2008, print thickness is 2.0mm;
Tensile property is tested: the tensile property testing sample by GB/T1040-2006, and draw speed is 50mm/min, and temperature is 25 DEG C;
Low temperature impact properties is tested: sample is placed 20min in the liquid nitrogen environment of-40 DEG C, does Charpy Impact;
DMA tests: adopt stretch mode, temperature scanning scope is-120 DEG C to 100 DEG C, and temperature rise rate is 10 DEG C/min.
Temperature limit of brittleness is tested: adopt MZ-4068 type rubber and plastic low-temperature brittleness test machine, test, batten size: long 20.00mm ± 0.25mm, wide 2.50mm ± 0.05mm, thick 2.00mm ± 0.1mm according to GB/T5470-2008;
Hardness test: the hardness of testing sample by GB/T531-2008.
Embodiment 1
By polyvinyl chloride (trade mark SG3, weight-average molecular weight is 170,000, be purchased from Tianjin organic chemical industry two factory), as 1 of softening agent, 2-cyclohexane cyclohexanedimethanodibasic dinonyl (trade mark hexamolldinch, be purchased from German BASF), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/1.5/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark NX-60A that shore hardness is 60A more wherein, be purchased from Taiwan Gao Ding chemical industry limited-liability company) 10 parts and quasi-styrene (trade mark LE, weight-average molecular weight is 80,000, synthetic materials factory is wished in Qinyang, Henan) 3 parts, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Embodiment 2
By polyvinyl chloride (trade mark SG4, weight-average molecular weight is 14.5 ten thousand, be purchased from Tianjin organic chemical industry two factory), as 1 of softening agent, 2-cyclohexane cyclohexanedimethanodibasic dinonyl (trade mark hexamolldinch, be purchased from German BASF), as the barium zinc composite stabilizer (model: BZ-8056 of stablizer, be purchased from Chuan Baoqi company limited of Shenzhen), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/2/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark NX-60A that shore hardness is 60A more wherein, be purchased from Taiwan Gao Ding chemical industry limited-liability company) 20 parts and quasi-styrene (trade mark C-10, weight-average molecular weight is 90,000, synthetic materials factory is wished in Qinyang, Henan) 5 parts, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Embodiment 3
By polyvinyl chloride (trade mark SG4, weight-average molecular weight is 14.5 ten thousand, be purchased from Tianjin organic chemical industry two factory), as the trimellitic acid three monooctyl ester (trade mark TOTM of softening agent, be purchased from Wujiang Jin Feng Chemical Co., Ltd.), as the barium cadmium Zn liquid composite stabilizing agent (model: BGX104-3 of stablizer, be purchased from Lian Feng Chemical Co., Ltd. of Rudong County), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/3/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark 460 that shore hardness is 70A more wherein, be purchased from Noveon company limited of the U.S.) 25 parts and quasi-styrene (trade mark C-10, weight-average molecular weight is 90,000, synthetic materials factory is wished in Qinyang, Henan) 6 parts, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Embodiment 4
By polyvinyl chloride (trade mark SG5, weight-average molecular weight is 130,000, be purchased from Tianjin organic chemical industry two factory), as the ATBC (trade mark ATBC of softening agent, be purchased from Jiangsu Leimeng Chemical Industry Science and Technology Co., Ltd), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/1.5/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark 67I70A that shore hardness is 70A more wherein, be purchased from safe polymer novel material company limited of Baoding nation) 10 parts and quasi-styrene (trade mark LE, weight-average molecular weight is 80,000, synthetic materials factory is wished in Qinyang, Henan) 3 parts, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Embodiment 5
By polyvinyl chloride (trade mark SG2, weight-average molecular weight is 190,000, be purchased from Tianjin organic chemical industry two factory), as 1 of softening agent, 2-cyclohexane cyclohexanedimethanodibasic dinonyl (trade mark hexamolldinch, be purchased from German BASF), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/2/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark 990R that shore hardness is 70A more wherein, be purchased from Bayer A.G) 15 parts and quasi-styrene (trade mark C-10, weight-average molecular weight is 90,000, and synthetic materials factory is wished in Qinyang, Henan) 5 parts, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Embodiment 6
By polyvinyl chloride (trade mark SG4, weight-average molecular weight is 14.5 ten thousand, be purchased from Tianjin organic chemical industry two factory), as 1 of softening agent, 2-cyclohexane cyclohexanedimethanodibasic dinonyl (trade mark hexamolldinch, be purchased from German BASF), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/3/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark 67I70A that shore hardness is 70A more wherein, be purchased from safe polymer novel material company limited of Baoding nation) 25 parts and quasi-styrene (trade mark C-10, weight-average molecular weight is 90,000, synthetic materials factory is wished in Qinyang, Henan) 6 parts, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Embodiment 7
By polyvinyl chloride (trade mark SG4, weight-average molecular weight is 14.5 ten thousand, be purchased from Tianjin organic chemical industry two factory), as 1 of softening agent, 2-cyclohexane cyclohexanedimethanodibasic dinonyl (trade mark hexamolldinch, be purchased from German BASF), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/25/3/2 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark S70A15 that shore hardness is 70A more wherein, be purchased from German BASF stock company) 5 parts and quasi-styrene (trade mark C-10, weight-average molecular weight is 90,000, synthetic materials factory is wished in Qinyang, Henan) 1 part, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Embodiment 8
By polyvinyl chloride (trade mark SG4, weight-average molecular weight is 14.5 ten thousand, be purchased from Tianjin organic chemical industry two factory), as 1 of softening agent, 2-cyclohexane cyclohexanedimethanodibasic dinonyl (trade mark hexamolldinch, be purchased from German BASF), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/45/3/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark C60A10WH that shore hardness is 60A more wherein, be purchased from German BASF stock company) 30 parts and quasi-styrene (trade mark C-10, weight-average molecular weight is 90,000, synthetic materials factory is wished in Qinyang, Henan) 10 parts, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Comparative example 9
By polyvinyl chloride (trade mark SG4, weight-average molecular weight is 14.5 ten thousand, be purchased from Tianjin organic chemical industry two factory), as 1 of softening agent, 2-cyclohexane cyclohexanedimethanodibasic dinonyl (trade mark hexamolldinch, be purchased from German BASF), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/3/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C of dischargings.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Comparative example 10
By polyvinyl chloride (trade mark SG4, weight-average molecular weight is 14.5 ten thousand, be purchased from Tianjin organic chemical industry two factory), as 1 of softening agent, 2-cyclohexane cyclohexanedimethanodibasic dinonyl (trade mark hexamolldinch, be purchased from German BASF), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/45/3/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark C60A10WH is purchased from German BASF stock company) 30 parts that shore hardness is 60A more wherein, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Comparative example 11
By polyvinyl chloride (trade mark SG4, weight-average molecular weight is 14.5 ten thousand, be purchased from Tianjin organic chemical industry two factory), as the trimellitic acid three monooctyl ester (trade mark TOTM of softening agent, be purchased from Wujiang Jin Feng Chemical Co., Ltd.), as the barium cadmium Zn liquid composite stabilizing agent (model: BGX-104-3 of stablizer, be purchased from Lian Feng Chemical Co., Ltd. of Rudong County), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/3/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add quasi-styrene (trade mark C-10, weight-average molecular weight is 90,000, and synthetic materials factory is wished in Qinyang, Henan) 6 parts more wherein, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Comparative example 12
By polyvinyl chloride (trade mark SG5, weight-average molecular weight is 130,000, be purchased from Tianjin organic chemical industry two factory), as the ATBC (trade mark ATBC of softening agent, be purchased from Jiangsu Leimeng Chemical Industry Science and Technology Co., Ltd), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/1.5/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark 67I70A that shore hardness is 70A more wherein, be purchased from safe polymer novel material company limited of Baoding nation) 2 parts and quasi-styrene (trade mark LE, weight-average molecular weight is 80,000, synthetic materials factory is wished in Qinyang, Henan) 3 parts, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
Comparative example 13
By polyvinyl chloride (trade mark SG3, weight-average molecular weight is 170,000, be purchased from Tianjin organic chemical industry two factory), as 1 of softening agent, 2-cyclohexane cyclohexanedimethanodibasic dinonyl (trade mark hexamolldinch, be purchased from German BASF), as the calcium-zinc composite stabilizing agent (model: GX-082 of stablizer, be purchased from Guangdong Dong Zheng Chemical Co., Ltd.), as the epoxy soybean oil (trade mark E-10 of extender plasticizer, being purchased from Guangzhou Xin Jinlong additives for plastics company limited) number with 100/35/1.5/5 weighs, add in homogenizer, first low speed (300r/min) stirs 4min, (1000r/min) stirs 10min at a high speed again, after reaching design temperature 100 DEG C, material is cooled to 60 DEG C.Add the polyester type TPU (trade mark NX-60A that shore hardness is 60A more wherein, be purchased from Taiwan Gao Ding chemical industry limited-liability company) 10 parts and quasi-styrene (trade mark LE, weight-average molecular weight is 80,000, synthetic materials factory is wished in Qinyang, Henan) 15 parts, keep 60-70 DEG C to mix 5-10min discharging.Then double roll mill is used by the mixing 10min of this mixture at the temperature of 165 DEG C, mixing evenly rear slice, cooling.Sheet material is cut out, and takes the cooling print of appropriate mass, put into mould, by vulcanizing/forming trier tabletted at 180 DEG C.After made print is placed more than 24h at normal temperatures, be cut into the required batten of experiment with universal sampling machine, carry out performance test to sample, experimental results is in table 1.
In upper table, transmittance and mist degree reflection be the properties of transparency of material, transmittance is larger, and mist degree is less, and the transparency of material is better; What low temperature impact strength reflected is material toughness at low ambient temperatures, what temperature limit of brittleness reflected is the minimum temperature that material does not produce destruction at low ambient temperatures, and this two indices all can reflect the cold tolerance of material, and low temperature impact strength is higher, temperature limit of brittleness is lower, and the winter hardiness of material is better; Plasticization temperature reflection material starts the temperature that plastic deformation occurs, and plasticization temperature is lower, and the processing temperature of material is lower, and polyvinyl chloride degree of decomposition in the course of processing is lower, and physical and mechanical properties is better.
Claims (12)
1. a polyvinyl chloride modifying material, the polyvinyl chloride (PVC) RESINS often comprising resin based on 100 weight parts in this material just comprises following component:
A) 1-10 weight part, the quasi-styrene of preferred 2-6 weight part, it is the graft copolymer of rubber or elastomerics and alpha-methyl styrene;
B) 5-30 weight part, the thermoplastic polyurethane of preferred 10-25 weight part;
C) thermo-stabilizer, preferred 1-4 weight part, the more preferably thermo-stabilizer of 1.5-3.5 weight part;
D) softening agent, preferred 20-50 weight part, is more preferably the softening agent of 25-35 weight part; With
E) optional extender plasticizer, preferred 1-6 weight part, is more preferably the extender plasticizer of 2-5 weight part,
Wherein each number is the parts by weight that polyvinyl chloride modifying material often comprises each component that 100 weight part polyvinyl chloride (PVC) RESINS comprise.
2. polyvinyl chloride modifying material as claimed in claim 1, the weight-average molecular weight of wherein said polyvinyl chloride (PVC) RESINS is 10-20 ten thousand, is preferably 12.5-15 ten thousand, especially for the trade mark of Tianjin organic chemical industry two factory is the polyvinyl chloride of SG3 and/or SG4.
3. polyvinyl chloride modifying material as claimed in claim 1 or 2, wherein said thermoplastic polyurethane is polyester type thermoplastic polyurethane.
4. the polyvinyl chloride modifying material according to any one of claim 1-3, wherein said thermoplastic polyurethane has the shore hardness of 60-70A; And/or the weight-average molecular weight of thermoplastic polyurethane is 200,000-28 ten thousand, be preferably 200,000-26 ten thousand.
5. the polyvinyl chloride modifying material according to any one of claim 1-4, the rubber or the elastomerics that wherein form described quasi-styrene are selected from paracril, vinyl-vinyl acetate copolymer elastomerics, ethylene-propylene rubber(EPR) and cis-1,4-polybutadiene rubber.
6. the polyvinyl chloride modifying material according to any one of claim 1-5, the weight-average molecular weight of wherein said quasi-styrene is 6-18 ten thousand, is preferably 7-10 ten thousand.
7. the polyvinyl chloride modifying material according to any one of claim 1-6, in wherein said quasi-styrene, the weight percentage of α-methylstyrenemonomer unit is 40%-80%, and the weight percentage of rubber or elastomeric monomers unit is 20%-60%; The weight percentage of preferred α-methylstyrenemonomer unit is 60%-80%, and the weight percentage of rubber or elastomeric monomers unit is 20%-40%; Particularly preferably described quasi-styrene is selected from the trade mark of wishing that synthetic materials factory produces in Qinyang, Henan is the quasi-styrene of C-10 and/or LE.
8. the polyvinyl chloride modifying material according to any one of claim 1-7, wherein said thermo-stabilizer be selected from lower group one or more: metal soap stablizer, liquid composite stabilizing agent and composition metal soap stablizer; Be preferably liquid composite stabilizing agent; Be more preferably the calcium-zinc composite stabilizing agent in liquid composite stabilizing agent.
9. the polyvinyl chloride modifying material according to any one of claim 1-8, wherein said softening agent be selected from lower group one or more: trimellitic acid three monooctyl ester (TOTM), tributyl citrate (TBC), tributyl acetylcitrate (ATBC), hexanaphthene-1,2-dioctyl phthalate diisononyl esters (DINCH) and hexanaphthene-1,2-dioctyl phthalate di-isooctyl (DEHCH); Preferred hexanaphthene-1,2-dioctyl phthalate diisononyl esters (DINCH).
10. polyvinyl chloride modifying material as claimed in any one of claims 1-9 wherein, wherein said auxiliary stabilizer is epoxy soybean oil (EOS).
11. 1 kinds of methods preparing the polyvinyl chloride modifying material according to any one of claim 1-10, comprise each component melts comprised by polyvinyl chloride modifying material and mediate; Preferably this melt kneading is carried out in twin screw extruder, this twin screw extruder has five sections of temperature control districts successively from opening for feed to discharge port, and every district temperature controls as follows: a district temperature 135-160 DEG C, two district temperature 135-155 DEG C, three district temperature 132-155 DEG C, four district temperature 130-150 DEG CHe five district temperature 130-148 DEG C.
12. polyvinyl chloride modifying materials according to any one of claim 1-10 at manufacture polyvinyl chloride hose, the purposes especially in transparent polyvinyl chloride flexible pipe.
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Cited By (4)
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| CN110408149A (en) * | 2019-08-21 | 2019-11-05 | 张媛婷 | A kind of high cold resistance polyvinyl chloride cable material and preparation method thereof |
| CN115710387A (en) * | 2022-09-08 | 2023-02-24 | 华美节能科技集团有限公司 | No-chlorinated paraffin rubber-plastic foaming thermal insulation material and preparation method thereof |
| CN115873358A (en) * | 2022-12-19 | 2023-03-31 | 金发科技股份有限公司 | Polyvinyl chloride composition and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924853A (en) * | 2016-06-24 | 2016-09-07 | 河南驼人医疗器械集团有限公司 | DEHCH-plasticized high-elasticity cold-resistant medical polyvinyl chloride granules and preparation method thereof |
| CN110408149A (en) * | 2019-08-21 | 2019-11-05 | 张媛婷 | A kind of high cold resistance polyvinyl chloride cable material and preparation method thereof |
| CN110408149B (en) * | 2019-08-21 | 2022-07-12 | 张媛婷 | High-cold-resistance polyvinyl chloride cable material and preparation method thereof |
| CN115710387A (en) * | 2022-09-08 | 2023-02-24 | 华美节能科技集团有限公司 | No-chlorinated paraffin rubber-plastic foaming thermal insulation material and preparation method thereof |
| CN115710387B (en) * | 2022-09-08 | 2024-01-30 | 华美节能科技集团有限公司 | Chlorinated paraffin-free rubber plastic foaming heat preservation material and preparation method thereof |
| CN115873358A (en) * | 2022-12-19 | 2023-03-31 | 金发科技股份有限公司 | Polyvinyl chloride composition and preparation method and application thereof |
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