CN102532763A - Chlorinated polrvinyl chloride modified material as well as preparation method and application thereof - Google Patents
Chlorinated polrvinyl chloride modified material as well as preparation method and application thereof Download PDFInfo
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- CN102532763A CN102532763A CN2011104434025A CN201110443402A CN102532763A CN 102532763 A CN102532763 A CN 102532763A CN 2011104434025 A CN2011104434025 A CN 2011104434025A CN 201110443402 A CN201110443402 A CN 201110443402A CN 102532763 A CN102532763 A CN 102532763A
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- polyvinyl chloride
- chlorinated polyvinyl
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title abstract 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 33
- 239000003063 flame retardant Substances 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 claims description 74
- 239000004801 Chlorinated PVC Substances 0.000 claims description 71
- 238000002156 mixing Methods 0.000 claims description 32
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 30
- 239000004800 polyvinyl chloride Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000004902 Softening Agent Substances 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 230000000979 retarding effect Effects 0.000 claims description 16
- -1 trimellitic acid SULPHOSUCCINIC ACID ESTER Chemical class 0.000 claims description 15
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005453 pelletization Methods 0.000 claims description 7
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- 229920013649 Paracril Polymers 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 2
- 239000001038 titanium pigment Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 2
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- 230000035939 shock Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 231100000517 death Toxicity 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a chlorinated polrvinyl chloride modified material as well as a preparation method and application thereof. The raw material formula of the chlorinated polrvinyl chloride modified material comprises the following components in parts by weight: 40-90 parts of chlorinated polrvinyl chloride, 20-70 parts of polrvinyl chloride, 5-30 parts of modified resin, 1.5-10 parts of heat stabilizing agent, 20-60 parts of plasticizer, 1-10 parts of antioxidant, 1-10 parts of lubricating agent, 5-40 parts of filling agent, 8-40 parts of fire retardant, 8-40 parts of flame retardant synergist and 1-20 parts of polrvinyl chloride processing aid. Compared with the known CPVC (chlorinated polrvinyl chloride) modified plastic, the CPVC modified plastic disclosed by the invention is more excellent in physical and mechanical properties and is relatively reduced in cost; and compared with the known CPVC modified plastic, the CPVC modified material disclosed by the invention is obviously improved in heat resistance and flame retardant property (oxygen index can reach about 45%, and simple root of CPVC modified material can be vertically burnt) besides more excellent processability and obviously improved material brittleness and shock resistance. Thus, the CPVC modified material disclosed by the invention is suitable for being used as a wire and cable sheath material.
Description
Technical field
The present invention relates to that a kind of to be suitable for making electric wire material modified and preparation method thereof with the chlorinated polyvinyl chloride of sheath.
Background technology
Because the flame-retardant sheath material of Cold-proof oilproof usually uses in harsh environmental conditions, as at high temperature, uses under the conditions such as intensive uviolizing, high ozone concentration, chemical corrosion; Some place; Top temperature can surpass 100 ℃, if cable does not reach above-mentioned described requirement, cable material is frangible even can decompose the cable sheath layer; All these situation can directly increase presence of fire or personnel's injures and deaths, and the risk that cable short circuit takes place simultaneously also can increase.
Chlorinated polyvinyl chloride resin (CPVC) is a further chlorating product of SE (PVC); Increase because of the polarity element; Its physicals, mechanical property; Resistance to heat distorsion particularly, high-low temperature resistant, erosion resistance, flame retardant properties etc. all are greatly improved than PVC, and heat resisting temperature is higher 30～40 ℃ than PVC; Be the better type material of a kind of over-all properties, have a wide range of applications at aspects such as tubing, coating and tamanori, foam materials, insulation and fire retardant material, man-made fibre material and sheet material, properties-correcting agent.Yet the CPVC resin also has its deficiency, and processing characteristics bad (processing temperature narrow range, melt viscosity is high, machine-shaping is difficult) is for example specifically arranged, and the big and shock resistance of fragility is relatively poor etc., and these deficiencies make its application be restricted.
In the prior art, the deficiency for the processibility that overcomes CPVC has proposed various improving one's methods.For example the open CN101704978A of Chinese invention patent discloses a kind of method that improves processability of chlorinated polyvinyl chloride resin; It is in the chlorinated polyvinyl chloride resin course of processing, to add thermoplastic polyurethane; Thereby improved the plasticizing capacity of chlorinated polyvinyl chloride resin in the course of processing; Reduce plasticization temperature, increase release property, thereby improved processibility.And for example; The open CN102250438A of Chinese invention patent discloses a kind of preparation method of chlorinated polyvinyl chloride modified plastics, and it comprises the steps: that (A) is with the nano imvite of 2～3 parts silane coupling agent and 100 parts combination treatment 10 minutes under 100 ℃, 3000 speed conditions; (B) 1～2 part lubricant, 3～5 parts the chlorinated polyvinyl chloride of one package stabilizer and 100 parts were mixed 6 minutes under 25 ℃, 3000 speed conditions; (c) will under 25 ℃, 3000 speed conditions, mix 6 minutes according to step (A) nano imvite of handling well and chlorinated polyvinyl chloride of handling well according to step (B); The mixture that will mix then melt extrudes in twin screw extruder broadcasts layer, obtains chlorinated polyvinyl chloride/Nano composite material of montmorillonite through tie rod, cooling, pelletizing; Each section of forcing machine TR is 160 ℃～190 ℃ when melt extruding intercalation, and screw speed is 50r/min; (D) chlorinated polyvinyl chloride/Nano composite material of montmorillonite of 100 parts and 7～8 parts PVC and 2～3 parts ACR processing aid are carried out the processing characteristics blending and modifying in twin screw extruder, again the footpath of the blend behind blending and modifying water-cooled, traction are obtained final chlorinated polyvinyl chloride modified plastics; Each section of twin screw extruder TR is 160 ℃～200 ℃ during blending and modifying, and screw speed is 50r/min.Chlorinated polyvinyl chloride modified plastics by the preparation of this method had both kept the high intensity and the characteristic of high heat resistance of CPVC, had reached the easy machining characteristics of general PVC material again.
As stated; Though proposed the method for the various CPVC of improvement processibilities; But these methods can not be simultaneously made good improvement to mechanical propertys such as the fragility of CPVC and shock resistances; Therefore, the CPVC behind these method improvements can not be suitable for well and make electric wire and cable jacket material (particularly under the severe environmental conditions).
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes prior art, provides a kind of chlorinated polyvinyl chloride material modified.
The present invention also will provide a kind of chlorinated polyvinyl chloride material modified preparation method simultaneously.
For solving the problems of the technologies described above, a kind of technical scheme that the present invention takes is:
A kind of chlorinated polyvinyl chloride is material modified, and in weight part, the material modified composition of raw materials of this chlorinated polyvinyl chloride is following: 40～90 parts of chlorinated polyvinyl chlorides; 20～70 parts of SE; 5～30 parts of modified resin; 1.5～10 parts of thermo-stabilizers; 20～60 parts in softening agent; 1～10 part in oxidation inhibitor; 1～10 part of lubricant; 5～40 parts of weighting agents; 8～40 parts of fire retardants; 1～20 part of 8～40 parts of fire retarding synergists and polyvinyl chloride processing aid; Wherein, described modified resin is for being selected from chlorinatedpolyethylene, paracril, acrylonitrile-styrene-acrylic ester (ABS) multipolymer and TEB 3K-butadiene-styrene ester (MBS) multipolymer one or more; Described thermo-stabilizer is for being selected from calcium-zinc composite stabilizing agent, soap type thermal stabilizing agent, rare earth class thermo-stabilizer, the organic tin thermo-stabilizer one or more; Described softening agent is to be selected from trimellitic acid SULPHOSUCCINIC ACID ESTER, epoxy soybean oil, dioctyl sebacate, DOP, the phthalic acid two different certain herbaceous plants with big flowers esters etc. one or more; Described weighting agent is to be selected from treated carbonates, talcum powder, silicon-dioxide, zeolite, white titanium pigment and the modified montmorillonoid one or more.
According to a concrete aspect of the present invention, the polymerization degree of employed chlorinated polyvinyl chloride is 500～1500, and the chlorine mass content is 61%～68% in the chlorinated polyvinyl chloride.
According to the present invention, oxidation inhibitor can be for being selected from one or more of phenolic antioxidant, amine antioxidants, thiobisphenol kind antioxidant and phosphite ester kind antioxidant.Lubricant can be for being selected from stearate, paraffin, OPE and the polyethylene wax one or more.Polyvinyl chloride processing aid can be acrylic polymer ACR-201, ACR-401 or their mixture.
Preferably, fire retardant is surface treated Antimony Trioxide: 99.5Min, white lake or white lake or their any mixture, and fire retarding synergist is zinc borate or ammonium molybdate or the mixture of the two.
Preferably, the material modified composition of raw materials of chlorinated polyvinyl chloride is following: 50～70 parts of chlorinated polyvinyl chlorides; 20～40 parts of SE; 8～20 parts of modified resin; 1.5～10 parts of thermo-stabilizers; 20～60 parts in softening agent; 1～5 part in oxidation inhibitor; 1～5 part of lubricant; 5～40 parts of weighting agents; 8～20 parts of fire retardants; 1～10 part of 8～20 parts of fire retarding synergists and polyvinyl chloride processing aid.
The another technical scheme that the present invention takes is: a kind of above-mentioned material modified preparation method of chlorinated polyvinyl chloride comprises the steps:
(1) by prescription, get chlorinated polyvinyl chloride, SE, modified resin, thermo-stabilizer, softening agent and add in the high-speed mixer, add lubricant after being mixed to 60～70 ℃; Fire retardant, fire retarding synergist, oxidation inhibitor; Weighting agent carries out mixed at high speed, after temperature rises to 90～110 ℃, adds polyvinyl chloride processing aid; Mixed at high speed, discharging is for use;
(2) step (1) gained material is dropped into two mixer mixings, get into two rank screw extrusion press through the bipyramid mixing roll again, mixing, extruding pelletization, it is material modified promptly to get said chlorinated polyvinyl chloride.
In an embodiment of method produced according to the present invention, each section of fuselage temperature of bipyramid mixing roll is followed successively by: 150 ℃～155 ℃, and 155 ℃～160 ℃, 160 ℃～165 ℃, 165 ℃～170 ℃, 170 ℃～175 ℃, 175 ℃～180 ℃; Head temperature is 180 ℃～185 ℃; Engine speed is 30 rev/mins, and the feeding rotating speed is 40 rev/mins.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
CPVC of the present invention is material modified is through with CPVC and PVC, modified resin blend, and adds that specific adjuvant is mixing to be obtained.Compare the material modified cost that has more superior physical and mechanical properties (particularly the fragility of material and shock resistance all are significantly improved) and reduce relatively of CPVC of the present invention with existing CPVC modified plastics; And compare with CPVC, the present invention is except fragility and shock resistance with more superior processibility and the material that significantly improves, and resistance toheat and flame retardant properties also significantly improve (oxygen index can reach about 45%, the single vertical combustion of crossing).Therefore, the material modified electric wire and cable jacket material that is suitable as very much of CPVC of the present invention.
Embodiment
Embodiment 1
Present embodiment provides a kind of chlorinated polyvinyl chloride material modified preparation method, and the raw material of employing is following:
CPVC: the polymerization degree is 1000, and cl content is 68%;
PVC：PVC?K：65；
Modified resin: chlorinatedpolyethylene;
Thermo-stabilizer: the mixture that calcium-zinc composite stabilizing agent and organotin stabilizer were formed by weight 3: 1;
Fire retardant: surface-treated Antimony Trioxide: 99.5Min (available from Anhua, Hunan Province China space antimony industry ltd);
Fire retarding synergist: zinc borate;
Lubricant: polyethylene wax;
Oxidation inhibitor: the compound system of four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, the two weight ratio is 1: 2;
Softening agent: the mixture of trimellitic acid SULPHOSUCCINIC ACID ESTER and epoxy soybean oil, the two weight ratio are 4: 1;
Weighting agent: treated carbonates;
The mixture of PVC processing aid: ACR-201 and ACR-401, the two weight ratio are 1: 1;
Said preparation method is specific as follows: according to the prescription of table 1, take by weighing chlorinated polyvinyl chloride, SE, modified resin, thermo-stabilizer, softening agent and add in the high-speed mixer, adding lubricant, fire retardant, fire retarding synergist, oxidation inhibitor and weighting agent after being mixed to 60～70 ℃ carries out mixed at high speed; Temperature rises to about 90～110 ℃ and to add the PVC processing aid, and mixed at high speed is about 1 minute, discharging; Drop into two mixer mixings, get into two rank screw extrusion press through the bipyramid mixing roll again and carry out mixing extruding pelletization, it is material modified promptly to get chlorinated polyvinyl chloride; When mixing, each section of fuselage temperature of bipyramid mixing roll is followed successively by: 150 ℃～155 ℃, and 155 ℃～160 ℃; 160 ℃～165 ℃; 165 ℃～170 ℃, 170 ℃～175 ℃, 175 ℃～180 ℃; Head temperature is 180 ℃～185 ℃; Engine speed is 30 rev/mins, and the feeding rotating speed is 40 rev/mins.
Embodiment 2
Present embodiment provides a kind of chlorinated polyvinyl chloride material modified preparation method, and the raw material of employing is following:
CPVC: the polymerization degree is 1000, and cl content is 63%;
PVC：PVC?K：65；
Modified resin: MBS;
Thermo-stabilizer: the mixture that calcium-zinc composite stabilizing agent and organotin stabilizer were formed by weight 2: 1;
Fire retardant: surface-treated Antimony Trioxide: 99.5Min (available from Anhua, Hunan Province China space antimony industry ltd);
Fire retarding synergist: ammonium molybdate;
Lubricant: polyethylene wax;
Oxidation inhibitor: the compound system of four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, the two weight ratio is 1: 2;
Softening agent: the mixture of trimellitic acid SULPHOSUCCINIC ACID ESTER, epoxy soybean oil and DOA, three's weight ratio are 3: 1: 1;
Weighting agent: treated carbonates;
The mixture of PVC processing aid: ACR-201 and ACR-401, the two weight ratio are 2: 1
Said preparation method is specific as follows: according to the prescription of table 1, take by weighing chlorinated polyvinyl chloride, SE, modified resin, thermo-stabilizer, softening agent and add in the high-speed mixer, adding lubricant, fire retardant, fire retarding synergist, oxidation inhibitor and weighting agent after being mixed to 60～70 ℃ carries out mixed at high speed; Temperature rises to about 90～110 ℃ and to add the PVC processing aid, and mixed at high speed is about 1 minute, discharging; Drop into two mixer mixings, get into two rank screw extrusion press through the bipyramid mixing roll again and carry out mixing extruding pelletization, it is material modified promptly to get chlorinated polyvinyl chloride; When mixing, each section of fuselage temperature of bipyramid mixing roll is followed successively by: 150 ℃～155 ℃, and 155 ℃～160 ℃; 160 ℃～165 ℃; 165 ℃～170 ℃, 170 ℃～175 ℃, 175 ℃～180 ℃; Head temperature is 180 ℃～185 ℃; Engine speed is 30 rev/mins, and the feeding rotating speed is 40 rev/mins.
Embodiment 3
Present embodiment provides a kind of chlorinated polyvinyl chloride material modified preparation method, and the raw material of employing is following:
CPVC: the polymerization degree is 1000, and cl content is 68%;
PVC：PVC?K：65；
Modified resin: chlorinatedpolyethylene
Thermo-stabilizer: calcium-zinc composite stabilizing agent;
Fire retardant: surface-treated Antimony Trioxide: 99.5Min (available from Anhua, Hunan Province China space antimony industry ltd)
Fire retarding synergist: the mixture that zinc borate and ammonium molybdate were formed by weight 2: 1;
Lubricant: microcrystalline wax;
Oxidation inhibitor: thiobisphenol kind antioxidant;
Softening agent: trioctyl trimellitate;
Weighting agent: treated carbonates;
The mixture of PVC processing aid: ACR-201 and ACR-401, the two weight ratio are 1: 1;
Said preparation method is specific as follows: according to the prescription of table 1, take by weighing chlorinated polyvinyl chloride, SE, modified resin, thermo-stabilizer, softening agent and add in the high-speed mixer, adding lubricant, fire retardant, fire retarding synergist, oxidation inhibitor and weighting agent after being mixed to 60～70 ℃ carries out mixed at high speed; Temperature rises to about 90～110 ℃ and to add the PVC processing aid, and mixed at high speed is about 1 minute, discharging; Drop into two mixer mixings, get into two rank screw extrusion press through the bipyramid mixing roll again and carry out mixing extruding pelletization, it is material modified promptly to get chlorinated polyvinyl chloride; When mixing, each section of fuselage temperature of bipyramid mixing roll is followed successively by: 150 ℃～155 ℃, and 155 ℃～160 ℃; 160 ℃～165 ℃; 165 ℃～170 ℃, 170 ℃～175 ℃, 175 ℃～180 ℃; Head temperature is 180 ℃～185 ℃; Engine speed is 30 rev/mins, and the feeding rotating speed is 40 rev/mins.
Embodiment 4
Present embodiment provides a kind of chlorinated polyvinyl chloride material modified preparation method, and the raw material of employing is following:
CPVC: the polymerization degree is 1000, and cl content is 68%;
PVC：PVC?K：65；
Modified resin: MBS;
Thermo-stabilizer: the mixture that calcium-zinc composite stabilizing agent and organotin stabilizer were formed by weight 1: 1;
Fire retardant: surface-treated Antimony Trioxide: 99.5Min (available from Anhua, Hunan Province China space antimony industry ltd);
Fire retarding synergist: zinc borate;
Lubricant: polyethylene wax;
Oxidation inhibitor: the compound system of four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, the two weight ratio is 1: 1;
Softening agent: the mixture of epoxy soybean oil and DOA, the two weight ratio are 1: 1;
Weighting agent: treated carbonates;
The mixture of PVC processing aid: ACR-201 and ACR-401, the two weight ratio are 2: 1;
Said preparation method is specific as follows: according to the prescription of table 1, take by weighing chlorinated polyvinyl chloride, SE, modified resin, thermo-stabilizer, softening agent and add in the high-speed mixer, adding lubricant, fire retardant, fire retarding synergist, oxidation inhibitor and weighting agent after being mixed to 60～70 ℃ carries out mixed at high speed; Temperature rises to about 90～110 ℃ and to add the PVC processing aid, and mixed at high speed is about 1 minute, discharging; Drop into two mixer mixings, get into two rank screw extrusion press through the bipyramid mixing roll again and carry out mixing extruding pelletization, it is material modified promptly to get chlorinated polyvinyl chloride; When mixing, each section of fuselage temperature of bipyramid mixing roll is followed successively by: 150 ℃～155 ℃, and 155 ℃～160 ℃; 160 ℃～165 ℃; 165 ℃～170 ℃, 170 ℃～175 ℃, 175 ℃～180 ℃; Head temperature is 180 ℃～185 ℃; Engine speed is 30 rev/mins, and the feeding rotating speed is 40 rev/mins.
The composition of raw materials unit of table 1 embodiment 1 to 4: weight part
Mechanical property and flame retardant resistance to the CPVC of the above embodiments 1 to 4 gained is material modified are tested, and the result sees table 2.
Table 2
Visible from table 2, the material modified intensity of CPVC according to the present invention, Good Heat-resistance be good flame resistance especially, and fragility is less, and shock resistance is good, satisfy electric wire and cable jacket material application requiring, and cost is low, has good economic and social benefit.
More than the present invention has been done detailed description; Its purpose is to let the personage that is familiar with this art can understand content of the present invention and implements; Can not limit protection scope of the present invention with this; And the invention is not restricted to the embodiments described, and all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. a chlorinated polyvinyl chloride is material modified, it is characterized in that: in weight part, the material modified composition of raw materials of said chlorinated polyvinyl chloride is following: 40 ~ 90 parts of chlorinated polyvinyl chlorides; 20 ~ 70 parts of SE; 5 ~ 30 parts of modified resin; 1.5 ~ 10 parts of thermo-stabilizers; 20 ~ 60 parts in softening agent; 1 ~ 10 part in oxidation inhibitor; 1 ~ 10 part of lubricant; 5 ~ 40 parts of weighting agents; 8 ~ 40 parts of fire retardants; 1 ~ 20 part of 8 ~ 40 parts of fire retarding synergists and polyvinyl chloride processing aid; Wherein, described modified resin is to be selected from chlorinatedpolyethylene, paracril, acrylonitrile-styrene-acrylic ester copolymer and TEB 3K-butadiene-styrene ester copolymer one or more; Described thermo-stabilizer is for being selected from calcium-zinc composite stabilizing agent, soap type thermal stabilizing agent, rare earth class thermo-stabilizer, the organic tin thermo-stabilizer one or more; Described softening agent is to be selected from trimellitic acid SULPHOSUCCINIC ACID ESTER, epoxy soybean oil, dioctyl sebacate, DOP, the phthalic acid two different certain herbaceous plants with big flowers esters etc. one or more; Described weighting agent is to be selected from treated carbonates, talcum powder, silicon-dioxide, zeolite, white titanium pigment and the modified montmorillonoid one or more.
2. chlorinated polyvinyl chloride according to claim 1 is material modified, it is characterized in that: the polymerization degree of described chlorinated polyvinyl chloride is 500 ~ 1500, and the chlorine mass content is 61% ~ 68% in the chlorinated polyvinyl chloride.
3. chlorinated polyvinyl chloride according to claim 1 is material modified, it is characterized in that: described oxidation inhibitor is to be selected from one or more of phenolic antioxidant, amine antioxidants, thiobisphenol kind antioxidant and phosphite ester kind antioxidant.
4. chlorinated polyvinyl chloride according to claim 1 is material modified; It is characterized in that: described fire retardant is surface treated Antimony Trioxide: 99.5Min, white lake or white lake or their any mixture, and described fire retarding synergist is zinc borate or ammonium molybdate or the mixture of the two.
5. chlorinated polyvinyl chloride according to claim 1 is material modified, it is characterized in that: described lubricant is to be selected from stearate, paraffin, OPE and the polyethylene wax one or more.
6. chlorinated polyvinyl chloride according to claim 1 is material modified, it is characterized in that: said polyvinyl chloride processing aid is acrylic polymer ACR-201, ACR-401 or their mixture.
7. material modified according to the described chlorinated polyvinyl chloride of each claim in the claim 1 to 6, it is characterized in that: the material modified composition of raw materials of described chlorinated polyvinyl chloride is following:: 50 ~ 70 parts of chlorinated polyvinyl chlorides; 20 ~ 40 parts of SE; 8 ~ 20 parts of modified resin; 1.5 ~ 10 parts of thermo-stabilizers; 20 ~ 60 parts in softening agent; 1 ~ 5 part in oxidation inhibitor; 1 ~ 5 part of lubricant; 5 ~ 40 parts of weighting agents; 8 ~ 20 parts of fire retardants; 1 ~ 10 part of 8 ~ 20 parts of fire retarding synergists and polyvinyl chloride processing aid.
8. the material modified preparation method of the described chlorinated polyvinyl chloride of each claim in the claim 1 to 7 is characterized in that: comprise the steps:
(1) by prescription, get chlorinated polyvinyl chloride, SE, modified resin, thermo-stabilizer, softening agent and add in the high-speed mixer, add lubricant after being mixed to 60 ~ 70 ℃; Fire retardant, fire retarding synergist, oxidation inhibitor; Weighting agent carries out mixed at high speed, after temperature rises to 90 ~ 110 ℃, adds polyvinyl chloride processing aid; Mixed at high speed, discharging is for use;
(2) step (1) gained material is dropped into two mixer mixings, get into two rank screw extrusion press through the bipyramid mixing roll again, mixing, extruding pelletization, it is material modified promptly to get said chlorinated polyvinyl chloride.
9. the material modified preparation method of chlorinated polyvinyl chloride according to claim 8 is characterized in that: each section of fuselage temperature of bipyramid mixing roll is followed successively by: 150 ℃ ~ 155 ℃, and 155 ℃ ~ 160 ℃; 160 ℃ ~ 165 ℃; 165 ℃ ~ 170 ℃, 170 ℃ ~ 175 ℃, 175 ℃ ~ 180 ℃; Head temperature is 180 ℃ ~ 185 ℃.
10. the material modified purposes that is used to make electric wire and cable jacket of the described chlorinated polyvinyl chloride of each claim in the claim 1 to 7.
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