CN113135999B - Toughening modifier for preparing polyvinyl chloride, polyvinyl chloride composition and application - Google Patents
Toughening modifier for preparing polyvinyl chloride, polyvinyl chloride composition and application Download PDFInfo
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 65
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 64
- 239000003607 modifier Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 30
- -1 polyethylene Polymers 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 8
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- 229920000573 polyethylene Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000005022 packaging material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 70
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 35
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 34
- 239000000460 chlorine Substances 0.000 claims description 34
- 229910052801 chlorine Inorganic materials 0.000 claims description 34
- 229920001903 high density polyethylene Polymers 0.000 claims description 34
- 239000004700 high-density polyethylene Substances 0.000 claims description 34
- 239000003999 initiator Substances 0.000 claims description 32
- 150000003254 radicals Chemical class 0.000 claims description 25
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000004094 surface-active agent Substances 0.000 claims description 21
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 18
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002612 dispersion medium Substances 0.000 claims description 3
- 239000004605 External Lubricant Substances 0.000 claims description 2
- 239000004610 Internal Lubricant Substances 0.000 claims description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 43
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid ester group Chemical group C(CCCCCCCCCCC)(=O)O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 18
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 16
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 239000005639 Lauric acid Substances 0.000 description 10
- 229920000193 polymethacrylate Polymers 0.000 description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- WNVCAMQMEDYSDX-UHFFFAOYSA-N butyl prop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical compound CCCCOC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 WNVCAMQMEDYSDX-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- CZXIDUCLWYWBLA-UHFFFAOYSA-N buta-1,3-diene hexyl 2-methylprop-2-enoate styrene Chemical compound C=CC=C.C=Cc1ccccc1.CCCCCCOC(=O)C(C)=C CZXIDUCLWYWBLA-UHFFFAOYSA-N 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229940125753 fibrate Drugs 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a toughening modifier for preparing polyvinyl chloride, a polyvinyl chloride composition and application, wherein the toughening modifier comprises chlorinated polyethylene, and the Mooney viscosity (ML (1+4) 125 ℃) of the chlorinated polyethylene is 5-40; the chlorinated polyethylene is obtained by the chlorination reaction of polyethylene, and the stirring speed is controlled to be 100-150 rpm in the chlorination reaction process. The polyvinyl chloride composition comprises 3-15 parts by weight of toughening modifier, 100 parts by weight of polyvinyl chloride resin, 0.8-3 parts by weight of stabilizer, 0.5-2 parts by weight of processing aid, 0.2-1 part by weight of inner lubricant and 0.1-0.5 part by weight of outer lubricant; the polyvinyl chloride composition can be applied to toys and packaging materials. The toughening modifier provided by the invention can obviously improve the transparency and toughness of the polyvinyl chloride product.
Description
Technical Field
The invention belongs to the technical field of preparation of polyvinyl chloride toughening modifiers, and particularly relates to a toughening modifier for preparing a polyvinyl chloride combination, a composition and application thereof.
Background
Polyvinyl chloride (PVC) has excellent mechanical properties, low cost, acid resistance, alkali resistance and corrosion resistance, and the processed polyvinyl chloride material has low residual monomer content and basically does not cause harm to human bodies. Therefore, polyvinyl chloride is also widely used in the fields of children's toys, packaging materials, and the like. However, polyvinyl chloride has a large brittleness and poor transparency, which limits the range of applications. In the exploration process, a terpolymer of styrene-hexyl methacrylate-butadiene (MBS) and a core-shell grafting copolymer of acrylic esters (AIM) are invented, so that the refractive index similar to that of a PVC matrix is achieved, and the impact performance of the product can be improved under the condition of affecting the transparency of the PVC as low as possible.
AIM has better processability and weather resistance, but in order to achieve refractive index close to that of PVC for AIM products, the impact resistance component is reduced, thus reducing the impact performance of the product; meanwhile, AIM belongs to a core-shell structure, so that intermolecular acting force among PVC molecules cannot be effectively reduced, the elongation at break of PVC products is not remarkably improved, and the requirements of customers on high toughness, such as the tearing strength index requirements of PVC calendered sheets or film products, cannot be met.
Although the MBS product has higher impact property, transparency and good processability, the MBS product has poorer weather resistance, is easy to age, decompose and change color under high temperature or illumination, and limits the application field of PVC transparent products; meanwhile, the MBS is easy to age when heated, so that the transparency of the product is affected; MBS also belongs to a core-shell structure, and the improvement of the elongation at break of PVC is not obvious, namely the toughness of PVC is not obviously improved.
The traditional Chlorinated Polyethylene (CPE) product has high elongation at break, can well improve the toughness of the product, and has the advantages of improved weather resistance and lower price because of no double bond. However, due to the dispersibility problem and the uniformity problem of the conventional chlorinated polyethylene, the transparency of the polyvinyl chloride product is seriously affected.
Disclosure of Invention
In view of the above, the invention provides a toughening modifier capable of obviously improving the transparency of a polyvinyl chloride product and improving the toughness of the polyvinyl chloride product.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the first aspect of the present invention provides a toughening modifier for preparing transparent polyvinyl chloride, the toughening modifier comprises chlorinated polyethylene, and the Mooney viscosity (ML (1+4) 125 ℃) of the chlorinated polyethylene is 5-40;
the chlorinated polyethylene is obtained by the chlorination reaction of polyethylene, and the stirring speed of the chlorination reaction is 100-150 rpm.
In some preferred embodiments, the chlorinated polyethylene has a Mooney viscosity (ML (1+4) 125 ℃) of 10 to 35, such as 15, 20, 28.
In a specific embodiment of the invention, the chlorinated polyethylene is prepared by the following method:
adding 35-60 parts by weight of polyethylene into 250-400 parts by weight of auxiliary agent to obtain a reaction solution; the chlorination reaction is carried out in stages under stirring;
a first stage reaction, wherein 8-30 parts by weight of chlorine is introduced into the reaction system, and the reaction is carried out for 1-2 hours, preferably 1-1.5 hours at 70-90 ℃;
the second stage reaction, in which 8-25 parts by weight of chlorine is continuously introduced, and the reaction is carried out for 1-2 hours, preferably 1-1.5 hours, at 120-140 ℃;
the third stage reaction, in which 8-25 parts by weight of chlorine is continuously introduced, and the reaction is carried out for 3-4 hours, preferably 3-3.5 hours, at 120-142 ℃;
and after the chlorination reaction is finished, cooling the temperature of the reaction system to below 40 ℃, centrifuging and drying to obtain the chlorinated polyethylene.
In some specific embodiments, the 250-400 parts by weight of the auxiliary agent comprises 0.2-1.0 parts by weight of dispersing agent, 0.1-0.5 parts by weight of emulsifying agent, 0.01-0.5 parts by weight of initiator and the balance of dispersing medium; preferably, 0.2 to 0.8 parts by weight of dispersant, 0.1 to 0.4 parts by weight of emulsifier, and 0.01 to 0.4 parts by weight of initiator. In the present invention, the dispersant, the emulsifier, the initiator and the dispersion medium mentioned can be all agents conventional in the art, for example, the dispersant can be sodium polymethacrylate, the emulsifier can be lauric acid polyoxyethylene ether, the initiator can be benzoyl peroxide or dicumyl peroxide, and the dispersion medium can be water.
In the invention, the chlorinated polyethylene is used as a toughening modifier of the polyvinyl chloride, and the Mooney viscosity (ML (1+4) 125 ℃) of the chlorinated polyethylene in the added toughening modifier is controlled to be 5-40, and the lower the Mooney viscosity is, the better the fluidity is; in some preferred embodiments, the chlorinated polyethylene has a Mooney viscosity (ML (1+4) 125 ℃) of 10 to 35, such as 15, 27.
In the invention, the chlorinated polyethylene is obtained by chlorination reaction of high-density polyethylene (HDPE abbreviated as English) with the density more than or equal to 0.95g/cm 3 For example, 0.95g/cm 3 ，0.98g/cm 3 . The research of the inventor finds that the weight average molecular weight and the molecular weight distribution index of the high-density polyethylene are one of factors influencing the Mooney viscosity of the chlorinated polyethylene, and when the weight average molecular weight Mw of the HDPE is in the range of 6 ten thousand to 12 ten thousand, for example, 8 ten thousand and 10 ten thousand; when the chlorinated polyethylene obtained through the chlorination reaction is used as a toughening modifier to be applied to a polyvinyl chloride product, the mechanical property and the optical property of the polyvinyl chloride product can be optimally balanced; when the weight average molecular weight Mw of HDPE is higher than 12 ten thousand, it is difficult to obtain chlorinated polyethylene having a low mooney viscosity, thereby affecting the flowability of the polyvinyl chloride product; however, when the weight average molecular weight Mw is less than 6 ten thousand, the mechanical properties of the polyvinyl chloride product are significantly lowered, and the impact resistance and toughness are lowered.
As a result of the study of the present inventors, it was found that when the molecular weight distribution index (M W d=mw/Mn) is between 2 and 6, e.g. 4,5; the broader the molecular weight distribution, the lower the mooney viscosity; when the viscosity is less than 2, the Mooney viscosity of the obtained chlorinated polyethylene is too high, and the fluidity is poor; when the particle size is higher than 6, a large amount of micromolecular wax substances exist in the HDPE, so that gaps of the particles can be melted and blocked in the chlorination process, the chlorination inside the particles is blocked, and the chlorination inside and outside the particles is uneven; meanwhile, the existence of small molecular wax substances can also obviously reduce the polyvinyl chloride productsMechanical properties of the alloy.
In the chlorination reaction process of the high-density polyethylene, chlorine gas permeates and chloridizes from outside to inside, and the limitation of the traditional production conditions (by adopting an enamel reactor) can not provide high enough stirring strength, so that the introduced chlorine gas can not uniformly disperse and coat HDPE; meanwhile, as the reaction temperature is increased, HDPE gradually agglomerates, and chlorine cannot permeate into the particles, so that the inside of the HDPE is not thoroughly chlorinated. Thus, the uniformity of the HDPE particles in contact with chlorine affects the chlorination effect of the chlorinated polyethylene. The inventor researches and discovers that the stirring speed of the high-density polyethylene in the chlorination reaction process is controlled to be 100-150 rpm, so that the HDPE can be fully contacted with chlorine in the chlorination reaction process, the chlorination effect is improved, the compatibility and the dispersibility of the HDPE with the polyvinyl chloride are further improved, and the transparency of the obtained polyvinyl chloride product is improved.
In the invention, the toughening modifier mainly comprises the following components in parts by weight, based on 100 parts by weight of the sum of A, B, C parts by weight of the toughening modifier:
a is 20 to 100 parts by weight of chlorinated polyethylene;
b is 0 to 60 parts by weight of a styrene-butadiene copolymer or a styrene-butadiene-methyl methacrylate copolymer;
c is 0 to 40 parts by weight of an alkyl acrylate-styrene-acrylonitrile copolymer or an alkyl acrylate;
wherein the alkyl acrylate is prepared from the following raw materials, and the weight sum of the raw materials (including n-butyl acrylate, methyl methacrylate and ethyl acrylate) is 100 percent, 10-40 percent of n-butyl acrylate, 40-90 percent of methyl methacrylate and 0-40 percent of ethyl acrylate;
the alkyl acrylate-styrene-acrylonitrile copolymer is prepared from the following raw materials (comprising n-butyl acrylate, methyl methacrylate, ethyl acrylate, styrene and acrylonitrile) by weight percent of 100 percent, wherein the raw materials comprise 8-40 percent of n-butyl acrylate, 0-70 percent of methyl methacrylate, 0-40 percent of ethyl acrylate, 20-70 percent of styrene and 1-25 percent of acrylonitrile.
In some preferred embodiments of the present invention, the toughening modifier is obtained by blending or polymerizing raw materials including the following components, wherein the sum of A, B, C parts by weight of the toughening modifier is 100:
a is 40-95 parts by weight of chlorinated polyethylene;
b is 4-40 parts by weight of a styrene-butadiene copolymer or a styrene-butadiene-methyl methacrylate copolymer;
c is 1-20 parts by weight of an alkyl acrylate-styrene-acrylonitrile copolymer or an alkyl acrylate;
in the present invention, when a certain component is 0 parts by weight, it means that the component is not contained; for example, when the weight part of the styrene-butadiene-methyl methacrylate copolymer or the styrene-butadiene copolymer is 0, or when the weight part of the alkyl acrylate-styrene-acrylonitrile copolymer or the alkyl acrylate is 0, it means that the above components are not added to the toughening modification obtained.
The above-mentioned polymerization method of alkyl acrylate may employ a method conventional in the art, for example, may be as follows:
10 to 40 percent of n-butyl acrylate, 40 to 90 percent of methyl methacrylate and 0 to 40 percent of ethyl acrylate are taken as polymerized monomers, wherein the sum of the weight of all the polymerized monomers is 100 percent; when the sum of the weight portions of the polymerized monomers is 100 portions, 100 to 200 portions of water, 0.5 to 4.0 portions of surfactant and 0.004 to 0.2 portions of free radical initiator are added into the mixture to react for 8 to 20 hours at the temperature of 50 to 85 ℃ and the stirring speed of 80 to 200rpm, so as to obtain the alkyl acrylate emulsion, and the corresponding alkyl acrylate is obtained after the drying treatment.
In the present invention, the alkyl acrylate-styrene-acrylonitrile copolymer may employ a technical method conventional in the art, for example, may be as follows:
10-40% of n-butyl acrylate, 0-70% of methyl methacrylate, 0-40% of ethyl acrylate, 20-70% of styrene and 1-25% of acrylonitrile, wherein the sum of the weight of all the polymerization monomers is 100%; for example, taking the polymerized monomer with the weight sum of 100, adding 100-200 parts by weight of water, 0.5-4.0 parts by weight of surfactant and 0.004-0.2 parts by weight of free radical initiator into the polymerized monomer, carrying out polymerization reaction for 8-20 hours at 50-85 ℃ and stirring speed of 50-500 rpm, and drying to obtain the alkyl acrylate-styrene-acrylonitrile copolymer;
in the present invention, the styrene-butadiene-methyl methacrylate copolymer may be directly obtained by purchasing commercially available products, for example, an impact modifier RK-730KP produced by Shandong Rike chemical production, or may be obtained by a conventional polymerization method using butadiene, styrene and methyl methacrylate as monomers; or the styrene-butadiene copolymer can be obtained by polymerization firstly and then is polymerized with methyl methacrylate, and the preparation method is used for reference as follows:
the first, it is obtained by polymerization reaction using butadiene, styrene and methyl methacrylate as monomer raw materials; calculated by the sum of the weight parts of the monomers as 100: 35-90 parts by weight of butadiene, 5-60 parts by weight of styrene and 5-30 parts by weight of methyl methacrylate; the specific operation mode belongs to the conventional operation in the field and is not repeated here;
second, first, a styrene-butadiene copolymer was prepared by the following method: adding 100-200 parts by weight of water, 0.5-4.0 parts by weight of surfactant and 0.2-0.5 parts by weight of free radical initiator into 100 parts by weight of styrene and butadiene monomers to carry out polymerization reaction for 12-32 hours under the conditions of 60-75 ℃ and stirring speed of 50-500 rpm, so as to obtain a styrene-butadiene copolymer; wherein the monomer is styrene or butadiene; of course, styrene-butadiene copolymers can also be prepared by other methods;
secondly, adding 4-40 parts by weight of styrene, 4-40 parts by weight of methyl methacrylate, 0.1-2 parts by weight of surfactant, 0.1-0.5 part by weight of free radical initiator and 0.1-0.5 part by weight of reducing agent into 40-80 parts by weight of the prepared styrene-butadiene copolymer, carrying out polymerization reaction for 3-5 h at the temperature of 60-75 ℃ and the stirring speed of 50-500 rpm, and drying or flocculating to obtain the styrene-butadiene-methyl methacrylate copolymer.
In some embodiments, the reducing agent is white powder, ferrous sulfate, sodium dithionite, or sodium bisulfite; the surfactant can be sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and modified alkyl alcohol polyether sulfonate; the free radical initiator may be potassium persulfate, sodium persulfate, etc.
In particular embodiments of the present invention, the toughening modifier may be reacted by blending or polymerization means in conventional techniques, for example, reference may be made to the means provided below:
20 to 100 parts by weight of chlorinated polyethylene; 0 to 60 parts by weight of a styrene-butadiene-methyl methacrylate copolymer or a styrene-butadiene copolymer; and blending 0-40 parts by weight of alkyl acrylate-styrene-acrylonitrile copolymer or alkyl acrylate to obtain the toughening modifier.
Or,
adding 20-100 parts by weight of chlorinated polyethylene into 0-60 parts by weight of styrene-butadiene-methyl methacrylate copolymer or styrene-butadiene copolymer, adding 0-200 parts by weight of water and 0.1-0.5 part by weight of free radical initiator, and then carrying out polymerization reaction at 50-70 ℃; continuously adding 0.2-2.5 parts by weight of surfactant, 0.1-0.3 part by weight of free radical initiator and 0-40 parts by weight of alkyl acrylate-styrene-acrylonitrile copolymer or alkyl acrylate into the mixture for polymerization reaction to obtain the toughening modifier.
Wherein the main components include chlorinated polyethylene, styrene-butadiene-methyl methacrylate copolymer or styrene-butadiene copolymer and alkyl acrylate-styrene-acrylonitrile copolymer or alkyl acrylate.
In a second aspect, the present invention provides a polyvinyl chloride composition comprising: 3 to 15 parts by weight of the toughening modifier, 100 parts by weight of the polyvinyl chloride resin, 0.8 to 3 parts by weight of the stabilizer, 0.5 to 2 parts by weight of the processing aid, 0.2 to 1 part by weight of the inner lubricant and 0.1 to 0.5 part by weight of the outer lubricant;
wherein the stabilizer is selected from one or more of an organotin stabilizer, a calcium zinc stabilizer or a lead salt stabilizer; the organotin stabilizer may be used in U.S. Pat. No. 181FS.
The processing aid and lubricant can be conventional agents in the art, and the processing aid can be one or more of acrylic polymers HPA-220, P-201 or PA-20 manufactured by Shandong Nissan chemical Co., ltd; the internal lubricant can be HG-60 and/or G-16, which are lubricants produced by Shandong Rike chemical Co., ltd; the external lubricant is selected from HG-74 and/or G-70S.
In the present invention, the polyvinyl chloride composition may be obtained by melt blending on an open mill, and specific operations are not described herein, as is well known to those skilled in the art.
In a third aspect, the invention provides the use of a polyvinyl chloride composition for toys and packaging materials.
By adopting the technical scheme, the method has the following technical effects:
according to the invention, the Mooney viscosity of the chlorinated polyethylene serving as the toughening modifier is controlled, so that the influence of the chlorinated polyethylene on the transparency of the polyvinyl chloride product is reduced, the fluidity of the chlorinated polyethylene is improved, and the transparency and toughness of the polyvinyl chloride product are obviously improved; meanwhile, the formula cost of the polyvinyl chloride transparent product is reduced.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples.
The raw materials used in the examples or comparative examples were all commercially available raw materials, specific information on a part of the raw materials is described below, products without information on suppliers are all reagents conventional in the art, and all purity specifications used are analytically pure.
High density polyethylene: HDPE, LG chemistry, density 0.95g/cm 3 ；
Organotin stabilizers: american road chemical TM181FS;
processing aid: HPA-220 of Shandong Rike chemical;
and (3) a lubricant: shandong Rike chemical, HG-60, HG-74;
dispersing agent: sodium polymethacrylate, county chemical industry Co., ltd;
emulsifying agent: lauric acid polyoxyethylene ether in Jiangsu province sea-An petrochemical plant;
polyvinyl chloride resin: tianjin Dagu chemical industry Co., ltd;
potassium persulfate: fang Jiaxin chemical industry Co., ltd;
dicumyl hydroperoxide: zibo win chemical industry Co., ltd;
sodium dodecyl benzene sulfonate: the celadon fibrate chemical group limited;
hanging powder: shanghai Bai chemical Co., ltd.
The test methods referred to in the following examples or comparative examples were as follows:
1. mooney viscosity: GB/T1232.1-2016;
2. transmittance: GB/T2410-2008;
3. haze: GB/T2410-2008;
4. elongation at break: GB/T528;
5. tensile strength: GB/T528;
6. QUV weatherability test: ASTM G154;
7、ΔE：ASTM G154。
example 1
Adding 0.3 weight parts of sodium polymethacrylate (dispersing agent), 0.25 weight parts of lauric acid polyoxyethylene ether (emulsifying agent) and 0.2 weight parts of dicumyl hydroperoxide (initiating agent) into a metal reactor, and then adding water to enable the total weight parts of the auxiliary agent to be 280; then adding 40 parts by weight of high-density polyethylene into the mixture to obtain a reaction solution; wherein the weight average molecular weight Mw of the high-density polyethylene is 6 ten thousand, and the molecular weight distribution index is 2;
the following chlorination reaction was carried out at a stirring speed of 125 rpm: the temperature of the first stage reaction is 80 ℃, and after the temperature is constant, 12 parts by weight of chlorine is introduced into the reaction liquid for reaction for 1.2 hours; after the first-stage reaction is completed, slowly raising the temperature of the system to 128 ℃ within 1 hour, continuously introducing 14 parts by weight of chlorine in the process of raising the temperature, and reacting for 1.3 hours; after the second-stage reaction is completed, continuously introducing 16 parts by weight of chlorine gas, and keeping the temperature of 128 ℃ for reaction for 3 hours; finally, the temperature of the system was cooled to 35℃and after centrifugation, the chlorinated polyethylene was obtained by drying at 70℃and was designated as sample 1.
Example 2
Adding 0.25 parts by weight of sodium polymethacrylate (dispersing agent), 0.3 parts by weight of lauric acid polyoxyethylene ether (emulsifying agent) and 0.28 parts by weight of dicumyl hydroperoxide (initiating agent) into a metal reactor, and then adding water to enable the total weight part of the auxiliary agent to be 250; then adding 36 parts by weight of high-density polyethylene into the mixture to obtain a reaction solution; wherein the weight average molecular weight Mw of the high-density polyethylene is 6 ten thousand, and the molecular weight distribution index is 6;
the following chlorination reaction was carried out at a stirring speed of 140 rpm: the temperature of the first-stage reaction is 78 ℃,13 parts by weight of chlorine is introduced into the reaction liquid after the temperature is constant, and the reaction is carried out for 1 hour; after the first-stage reaction is completed, slowly heating the system to 126 ℃ within 1 hour, introducing 12 parts by weight of chlorine in the heating process, and reacting for 1.2 hours; after the second-stage reaction is completed, 13 parts by weight of chlorine is continuously introduced, and the reaction is kept at the temperature of 126 ℃ for 3 hours; finally, the temperature of the system was cooled to 35 ℃, centrifuged and dried at 70 ℃ to obtain chlorinated polyethylene, designated as sample 2.
Example 3
Adding 0.4 parts by weight of sodium polymethacrylate (dispersing agent), 0.33 parts by weight of lauric acid polyoxyethylene ether (emulsifying agent) and 0.3 parts by weight of dicumyl hydroperoxide (initiator) into a metal reactor, and then adding water to enable the total weight part of the auxiliary agent to be 320; then 56 parts by weight of high-density polyethylene is added into the mixture to obtain a reaction solution; wherein the weight average molecular weight Mw of the high-density polyethylene is 12 ten thousand, and the molecular weight distribution index is 6.
The following chlorination reaction was carried out at a stirring speed of 125 rpm: the temperature of the first stage reaction is 84 ℃, 18 parts by weight of chlorine is introduced into the reaction liquid after the temperature is constant, and the reaction is carried out for 1.5 hours; after the first-stage reaction is completed, slowly raising the temperature of the system to 136 ℃ within 1 hour, introducing 17 parts by weight of chlorine in the process of raising the temperature, and reacting for 1 hour; after the second-stage reaction is completed, continuously introducing 25 parts by weight of chlorine, and keeping the temperature of 126 ℃ for reaction for 3 hours; finally, the temperature of the system was cooled to 35 ℃, centrifuged and dried at 70 ℃ to obtain chlorinated polyethylene, designated as sample 3.
Example 4
Adding 0.5 weight parts of sodium polymethacrylate (dispersing agent), 0.1 weight parts of lauric acid polyoxyethylene ether (emulsifying agent) and 0.25 weight parts of dicumyl hydroperoxide (initiating agent) into a metal reactor, and then adding water to enable the total weight parts of the auxiliary agent to be 300; then 54 parts by weight of high-density polyethylene is added into the mixture to obtain a reaction solution; wherein the weight average molecular weight Mw of the high-density polyethylene is 8 ten thousand, and the molecular weight distribution index is 4.
The following chlorination reaction was carried out at a stirring speed of 130 rpm: the temperature of the first stage reaction is 82 ℃, and after the temperature is constant, 16 parts by weight of chlorine is introduced into the reaction liquid for reaction for 1.4 hours; after the first-stage reaction is completed, slowly heating the system to 132 ℃ within 1 hour, introducing 19 parts by weight of chlorine in the heating process, and reacting for 1.5 hours; after the second-stage reaction is completed, continuously introducing 25 parts by weight of chlorine, and keeping the temperature of 136 ℃ for reaction for 3 hours; finally, the temperature of the system was cooled to 35 ℃, centrifuged and dried at 70 ℃ to obtain chlorinated polyethylene, designated as sample 4.
Example 5
Adding 0.55 parts by weight of sodium polymethacrylate (dispersing agent), 0.26 parts by weight of lauric acid polyoxyethylene ether (emulsifying agent) and 0.4 parts by weight of dicumyl hydroperoxide (initiating agent) into a metal reactor, and then adding water to enable the total weight part of the auxiliary agent to be 280; then 48 parts by weight of high-density polyethylene is added into the mixture to obtain a reaction solution; wherein the weight average molecular weight Mw of the high-density polyethylene is 8 ten thousand, and the molecular weight distribution index is 6.
The following chlorination reaction was carried out at a stirring speed of 130 rpm: the temperature of the first stage reaction is 80 ℃, 19 parts by weight of chlorine is introduced into the reaction liquid after the temperature is constant, and the reaction is carried out for 1.2 hours; after the first-stage reaction is completed, slowly heating the system to 132 ℃ within 1 hour, introducing 12 parts by weight of chlorine in the heating process, and reacting for 1.4 hours; after the second-stage reaction is completed, continuously introducing 20 parts by weight of chlorine, and keeping the temperature of 130 ℃ for reaction for 3 hours; finally, the temperature of the system was cooled to 35 ℃, centrifuged and dried at 70 ℃ to obtain chlorinated polyethylene, designated as sample 5.
Example 6
Adding 0.57 weight parts of sodium polymethacrylate (dispersing agent), 0.32 weight parts of lauric acid polyoxyethylene ether (emulsifying agent) and 0.33 weight parts of dicumyl hydroperoxide (initiating agent) into a metal reactor, and then adding water to enable the total weight parts of the auxiliary agent to be 380; then 60 parts by weight of high-density polyethylene is added into the mixture to obtain a reaction solution; wherein the weight average molecular weight Mw of the high-density polyethylene is 12 ten thousand, and the molecular weight distribution index is 4.
The following chlorination reaction was carried out at a stirring speed of 145 rpm: the temperature of the first stage reaction is 88 ℃, 18 parts by weight of chlorine is introduced into the reaction liquid after the temperature is constant, and the reaction is carried out for 1.5 hours; after the first-stage reaction is completed, slowly raising the temperature of the system to 138 ℃ within 1 hour, introducing 22 parts by weight of chlorine in the process of raising the temperature, and reacting for 1.1 hour; after the second-stage reaction is completed, continuously introducing 24 parts by weight of chlorine, and keeping the temperature of 130 ℃ for reaction for 3 hours; finally, the temperature of the system was cooled to 35 ℃, centrifuged and dried at 70 ℃ to obtain chlorinated polyethylene, designated sample 6.
Comparative example 1
Adding 1.0 weight part of sodium polymethacrylate (dispersing agent), 0.5 weight part of lauric acid polyoxyethylene ether (emulsifying agent) and 0.38 weight part of dicumyl peroxide (initiating agent) into an enamel reactor, and then adding water to ensure that the total weight part of the auxiliary agent is 260; then adding 45 parts by weight of high-density polyethylene into the mixture to obtain a reaction solution; wherein the weight average molecular weight Mw of the high-density polyethylene is 8 ten thousand, and the molecular weight distribution index is 4.
The following chlorination reaction was carried out at a stirring speed of 75 rpm: the temperature of the first stage reaction is 80 ℃, 18 parts by weight of chlorine is introduced into the reaction liquid after the temperature is constant, and the reaction is carried out for 1.5 hours; after the first-stage reaction is completed, slowly heating the system to 130 ℃ within 1 hour, introducing 16 parts by weight of chlorine in the heating process, and reacting for 1.5 hours; after the second-stage reaction is completed, 14 parts by weight of chlorine is continuously introduced, and the reaction is kept at the temperature of 130 ℃ for 3 hours; finally, the temperature of the system was cooled to 35 ℃, centrifuged and dried at 70 ℃ to obtain chlorinated polyethylene, designated as comparative sample 1.
Comparative example 2
Adding 0.6 weight parts of sodium polymethacrylate (dispersing agent), 0.4 weight parts of lauric acid polyoxyethylene ether (emulsifying agent) and 0.36 weight parts of dicumyl hydroperoxide (initiating agent) into a metal reactor, and then adding water to enable the total weight parts of the auxiliary agent to be 300; then 56 parts by weight of high-density polyethylene is added into the mixture to obtain a reaction solution; wherein the weight average molecular weight Mw of the high-density polyethylene is 20 ten thousand, and the molecular weight distribution index is 6.
The following chlorination reaction was carried out at a stirring speed of 125 rpm: the temperature of the first stage reaction is 90 ℃, and after the temperature is constant, 20 parts by weight of chlorine is introduced into the reaction liquid for reaction for 1.3 hours; after the first-stage reaction is completed, slowly heating the temperature of the system to 140 ℃ within 1 hour, introducing 25 parts by weight of chlorine in the heating process, and reacting for 1.2 hours; after the second-stage reaction is completed, continuously introducing 15 parts by weight of chlorine gas, and keeping the temperature of 140 ℃ for reaction for 3 hours; finally, the temperature of the system was cooled to 35 ℃, centrifuged and dried at 70 ℃ to obtain chlorinated polyethylene, designated as comparative sample 2.
The samples 1-6 and the comparative samples 1 and 2 are used as toughening modifier components in the preparation process of the polyvinyl chloride product, and are proportioned according to the following parts by weight:
(a) Taking 100 parts by weight of polyvinyl chloride resin;
(b) Adding 5 parts by weight of the toughening modifier sample to the polyvinyl chloride resin in the step (a);
(c) Continuously adding 1.2 parts by weight of an organotin stabilizer;
(d) 1 part by weight of a processing aid HPA-220 for polyvinyl chloride products;
(e) 0.5 parts by weight of an inner lubricant HG-60,0.5 parts by weight of an outer lubricant HG-74.
The components are subjected to open refining on a two-roll open mill at 185 ℃ for 5 minutes, rolled sheets are cut into rectangles of 9cm multiplied by 20cm after the open refining is finished, the rectangles are placed into a die, a pressing plate is arranged in a flat vulcanizing machine, and a sample is prepared after a plate with the thickness of 3mm is pressed out, so that a polyvinyl chloride product is obtained.
Preparing 6-8 impact splines of 8cm multiplied by 1cm and dumbbell-shaped tensile splines of 15cm multiplied by 2cm respectively from the product, and performing performance test on the splines; specific data of properties of chlorinated polyethylene obtained under different preparation conditions and polyvinyl chloride products prepared from the chlorinated polyethylene are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the Mooney viscosities of the chlorinated polyethylene samples 1 to 6 are low, and the stirring strengths during the chlorination reaction are controlled within the range of 100 to 150rpm, which is advantageous for obtaining polyvinyl chloride products with good optical properties. As is clear from comparison with comparative example 1, the stirring strength is low, the internal chlorination effect of the polyethylene particles is poor, and also the non-chlorinated HDPE and chlorinated polyethylene components having a low degree of chlorination are poor in compatibility with polyvinyl chloride, and the light transmittance of these components is inconsistent, resulting in a polyvinyl chloride product having high haze and poor transparency.
Example 7
Preparation of styrene-butadiene copolymer: adding 10 parts by weight of styrene, 90 parts by weight of butadiene and 100 parts by weight of water into a closed reactor, continuously adding 2.1 parts by weight of sodium dodecyl benzene sulfonate (surfactant) and 0.25 part by weight of potassium persulfate (free radical initiator), and reacting for 15 hours at the stirring speed of 64 ℃ and 130rpm to obtain an emulsion of a styrene-butadiene copolymer;
adding 120 parts by weight of water, 3.3 parts by weight of sodium dodecyl benzene sulfonate (surfactant) and 0.1 part by weight of potassium persulfate (free radical initiator) into 30 parts by weight of n-butyl acrylate and 70 parts by weight of methyl methacrylate, simultaneously adding into a reactor, heating to 54 ℃ at a stirring speed of 120rpm, and reacting for 12 hours to obtain an alkyl acrylate emulsion;
50 parts by weight of chlorinated polyethylene (sample 4) was added to 40 parts by weight of the emulsion of the above styrene-butadiene copolymer, stirring was started, the temperature was gradually raised to 65℃and 0.5 part by weight of potassium persulfate as a radical initiator was added thereto for polymerization for 3 hours; then, the mixture was kept at 70℃and further polymerized by adding 1.5 parts by weight of sodium dodecylbenzenesulfonate (surfactant), 0.16 parts by weight of potassium persulfate (radical initiator) and 10 parts by weight of alkyl acrylate emulsion for 5 hours, and then cooled to 35℃and dried at 70℃to obtain a toughening modifier powder, which was designated as sample 7, having a conversion of 98.65%.
Example 8
Preparation of styrene-butadiene copolymer: adding 18 weight parts of styrene, 82 weight parts of butadiene and 100 weight parts of water into a closed reactor, continuously adding 1.8 weight parts of sodium dodecyl benzene sulfonate (surfactant) and 0.4 weight parts of potassium persulfate (free radical initiator), and reacting for 16 hours at 68 ℃ at a stirring speed of 110rpm to obtain an emulsion of a styrene-butadiene copolymer;
preparation of n-butyl acrylate-styrene-acrylonitrile copolymer:
adding 100 parts by weight of water into 40 parts by weight of n-butyl acrylate, 40 parts by weight of styrene and 20 parts by weight of acrylonitrile, continuously adding 1.8 parts by weight of sodium dodecyl benzene sulfonate (surfactant) and 0.1 part by weight of potassium persulfate (free radical initiator), polymerizing at 70 ℃ for 15 hours at 200rmp, and drying to obtain an n-butyl acrylate-styrene-acrylonitrile copolymer;
50 parts by weight of chlorinated polyethylene (sample 4) was put into 40 parts by weight of the emulsion of the above styrene-butadiene copolymer, stirring was started, the temperature was gradually raised to 60℃and 0.4 part by weight of potassium persulfate as a radical initiator was added thereto for polymerization for 3 hours; then, the mixture was kept at 68℃and was further added with 1.4 parts by weight of sodium dodecylbenzenesulfonate (surfactant), 0.18 parts by weight of potassium persulfate (radical initiator) and 10 parts by weight of n-butyl acrylate-styrene-acrylonitrile copolymer, followed by copolymerization for 4 hours, cooling to 35℃and drying at 70℃to obtain a toughening modifier powder, which was designated as sample 8, having a conversion of 98.77%.
Example 9
Adding 120 parts by weight of water, 3.3 parts by weight of sodium dodecyl benzene sulfonate (surfactant) and 0.1 part by weight of potassium persulfate (free radical initiator) into 30 parts by weight of n-butyl acrylate and 70 parts by weight of methyl methacrylate, simultaneously adding into a reactor, heating to 54 ℃ at a stirring speed of 120rpm, and reacting for 12 hours to obtain an alkyl acrylate emulsion;
80 parts by weight of chlorinated polyethylene (sample 4) was added with 20 parts by weight of the above alkyl acrylate and 100 parts by weight of water, 2.2 parts by weight of sodium dodecylbenzenesulfonate (surfactant) and 0.45 parts by weight of potassium persulfate (radical initiator) were simultaneously added to a closed reactor, heated to 52℃with a stirring speed of 800rpm, polymerized for 12 hours, cooled to 35℃and dried at 70℃to give a toughening modifier powder, designated sample 9, having a conversion of 98.16%.
Example 10
Preparation of styrene-butadiene-methyl methacrylate copolymer:
15 parts by weight of styrene, 85 parts by weight of butadiene and 120 parts by weight of water, 1.7 parts by weight of sodium dodecylbenzenesulfonate (surfactant) and 0.3 parts by weight of potassium persulfate (radical initiator) were charged into a closed reactor and reacted at 72℃for 14 hours at a stirring speed of 75rpm to obtain an emulsion of a styrene-butadiene copolymer; then, to the above-mentioned emulsion of 68 parts by weight of styrene-butadiene copolymer were added 12 parts by weight of styrene, 20 parts by weight of methyl methacrylate, 1.0 part by weight of sodium dodecylbenzenesulfonate (surfactant), 0.33 parts by weight of potassium persulfate (radical initiator) and 0.33 parts by weight of white powder (reducing agent), and the mixture was heated to 75℃at a stirring speed of 113rpm, and polymerized for 3 hours to obtain an emulsion of styrene-butadiene-methyl methacrylate copolymer, which was dried at 70℃to obtain a styrene-butadiene-methyl methacrylate copolymer, designated as sample 10;
18 parts by weight of n-butyl acrylate, 60 parts by weight of methyl methacrylate, 22 parts by weight of ethyl acrylate as a polymerization monomer, 120 parts by weight of water, 3.6 parts by weight of sodium dodecylbenzenesulfonate (surfactant) and 0.1 part by weight of potassium persulfate (radical initiator) were simultaneously added to a reactor, and the mixture was heated to 54℃under stirring at 120rpm to react for 12 hours, and dried to obtain alkyl acrylate, which was designated as sample 11;
40 parts by weight of sample 4, 40 parts by weight of sample 10 and 20 parts by weight of sample 11 were blended to obtain a toughening modifier powder, designated as sample 12.
Example 11
Preparation of styrene-butadiene-methyl methacrylate copolymer:
adding 20 parts by weight of styrene, 80 parts by weight of butadiene and 140 parts by weight of water, 2.8 parts by weight of sodium dodecyl benzene sulfonate (surfactant) and 0.31 part by weight of potassium persulfate (free radical initiator) into a closed reactor, heating to 70 ℃ at a stirring speed of 95rpm, and carrying out polymerization for 10 hours to obtain an emulsion of a styrene-butadiene copolymer;
then, 10 parts by weight of styrene, 15 parts by weight of methyl methacrylate, 1.8 parts by weight of sodium dodecylbenzenesulfonate (surfactant), 0.25 parts by weight of potassium persulfate (radical initiator) and 0.25 parts by weight of white powder (reducing agent) were added to the emulsion of the above 75 parts by weight of styrene-butadiene copolymer, and the mixture was heated to 74℃at a stirring speed of 165rpm to polymerize the mixture for 3 hours to obtain an emulsion of styrene-butadiene-methyl methacrylate copolymer, which was dried at 70℃to obtain a styrene-butadiene-methyl methacrylate copolymer, which was designated as sample 13;
60 parts by weight of sample 1 and 40 parts by weight of sample 13 were blended to obtain a toughening modifier powder, designated as sample 14.
Example 12
To 22 parts by weight of butyl acrylate, 65 parts by weight of styrene and 13 parts by weight of acrylonitrile were added 150 parts by weight of water, 0.6 parts by weight of sodium dodecylbenzenesulfonate (surfactant) and 0.08 parts by weight of potassium persulfate (radical initiator), and the mixture was heated to 55℃with stirring at 225rpm to polymerize for 16 hours, and then dried to obtain a butyl acrylate-styrene-acrylonitrile copolymer, which was designated as sample 15.
80 parts by weight of sample 2 was blended with 20 parts by weight of sample 15 to give a toughening modifier powder, designated sample 16.
Comparative example 3
60 parts by weight of comparative sample 2 (comparative example 2) was blended with 40 parts by weight of sample 10 (example 10) to give a toughening modifier powder, designated comparative sample 3.
Comparative example 4
Sample 10, designated comparative sample 4, was prepared as described in example 10.
The samples 4, 7-9, 12, 13, 16 and the comparative samples 3, 4 are proportioned according to the following weight parts to obtain products 4, 7-9, 12, 13, 16 and comparative products 3, 4:
(a) Taking 100 parts by weight of polyvinyl chloride resin;
(b) Adding 5 parts by weight of the toughening modifier sample obtained above to the polyvinyl chloride resin in step (a);
(c) Continuously adding 1.2 parts by weight of an organotin stabilizer;
(d) 1 part by weight of a processing aid HPA-220 for PVC products;
(e) 1 part by weight of lubricant HG-60,0.5 parts by weight of lubricant HG-74.
The components are subjected to open refining on a two-roll open mill at 185 ℃ for 5 minutes, the pressed sheet is cut into a rectangle of 9cm multiplied by 20cm after the open refining is finished, the rectangle is put into a die, a pressing plate is arranged in a flat vulcanizing machine, and a sample is prepared after a plate with the thickness of 3mm is pressed out, so that a polyvinyl chloride product is obtained.
Preparing 6-8 impact splines of 8cm multiplied by 1cm and dumbbell-shaped tensile splines of 15cm multiplied by 2cm respectively from the product, and performing performance test on the splines; specific data of the properties of the polyvinyl chloride products obtained under different preparation conditions are shown in Table 2.
TABLE 2
Through QUV weather resistance experiments, the larger the color value change condition delta E after product testing is obtained, the worse the weather resistance of the product is, the more yellowing is easy to happen under the irradiation of light; the plasticizing time is characterized by the gelation time of the polyvinyl chloride mixture, and the shorter the time is, the better the plasticizing effect is, and the promoting effect on the dispersion of the modifier is achieved.
As can be seen from the data in Table 2, when the toughening modifier of the present invention is added into the polyvinyl chloride product, the light transmittance of the product is obviously improved, the weather resistance of the product is obviously improved, the color value change is not obvious, and the product is favorable for outdoor use.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (11)
1. The toughening modifier for preparing the polyvinyl chloride is characterized by comprising chlorinated polyethylene, wherein the Mooney viscosity (ML (1+4) 125 ℃) of the chlorinated polyethylene is 20-40;
the chlorinated polyethylene is obtained by chlorination reaction of polyethylene, and is prepared by the following method:
adding 35-60 parts by weight of polyethylene into 250-400 parts by weight of auxiliary agent to obtain reaction liquid, and stirring to carry out chlorination reaction in stages; the stirring speed is 100-150 rpm;
in the first stage, 8-30 parts by weight of chlorine is introduced into the reaction system, and the reaction is carried out for 1-2 hours at 70-90 ℃;
the second stage reaction, continuously introducing 8-25 parts by weight of chlorine, and reacting for 1-2 hours at 120-140 ℃;
in the third stage, 8-25 parts by weight of chlorine is continuously introduced, and the reaction is carried out for 3-4 hours at 120-142 ℃;
the weight average molecular weight of the polyethylene is 8-12 ten thousand, and the molecular weight distribution index is 4-6.
2. The toughening modifier according to claim 1, wherein the chlorinated polyethylene has a mooney viscosity (ML (1+4) 125 ℃) of 20 to 35.
3. The toughening modifier according to claim 1, wherein in the method for producing chlorinated polyethylene,
in the first stage, 8-30 parts by weight of chlorine is introduced into the reaction system, and the reaction is carried out for 1-1.5 hours at 70-90 ℃;
the second stage reaction, continuously introducing 8-25 parts by weight of chlorine, and reacting for 1-1.5 hours at 120-140 ℃;
in the third stage, 8-25 parts by weight of chlorine is continuously introduced, and the reaction is carried out for 3-3.5 hours at 120-142 ℃;
and after the chlorination reaction is finished, cooling the temperature of the reaction system to below 40 ℃, centrifuging and drying to obtain the chlorinated polyethylene.
4. A toughening modifier according to claim 3, wherein the auxiliary agent in the range of 250 to 400 parts by weight comprises 0.2 to 1.0 part by weight of dispersant, 0.1 to 0.5 part by weight of emulsifier, 0.01 to 0.5 part by weight of initiator, and the balance being dispersion medium.
5. The toughening modifier according to claim 4, wherein the auxiliary agent of 250 to 400 parts by weight comprises 0.2 to 0.8 part by weight of a dispersant, 0.1 to 0.4 part by weight of an emulsifier, and 0.01 to 0.4 part by weight of an initiator.
6. The toughening modifier according to claim 1, wherein the polyethylene is a high density polyethylene having a density of 0.95g/cm or more 3 。
7. The toughening modifier according to any one of claims 1 to 6, wherein the toughening modifier mainly comprises the following components, based on the sum of A, B, C parts by weight of the toughening modifier as 100:
a is 20 to 100 parts by weight of chlorinated polyethylene;
b is 0 to 60 parts by weight of a styrene-butadiene copolymer or a styrene-butadiene-methyl methacrylate copolymer;
c is 0 to 40 parts by weight of an alkyl acrylate-styrene-acrylonitrile copolymer or an alkyl acrylate;
wherein, the alkyl acrylate is prepared from the following raw materials, 10-40% of n-butyl acrylate, 40-90% of methyl methacrylate and 0-40% of ethyl acrylate by taking the sum of the weight of the raw materials as 100%;
the alkyl acrylate-styrene-acrylonitrile copolymer is prepared from the following raw materials, by weight, based on 100% of the sum of the raw materials, 8-40% of n-butyl acrylate, 0-70% of methyl methacrylate, 0-40% of ethyl acrylate, 20-70% of styrene and 1-25% of acrylonitrile.
8. The toughening modifier according to claim 7, wherein the toughening modifier is prepared by the following method:
20 to 100 parts by weight of chlorinated polyethylene; 0 to 60 parts by weight of a styrene-butadiene-methyl methacrylate copolymer or a styrene-butadiene copolymer; and blending 0-40 parts by weight of alkyl acrylate-styrene-acrylonitrile copolymer or alkyl acrylate to obtain the toughening modifier.
9. The toughening modifier according to claim 7, wherein the toughening modifier is prepared by the following method:
adding 20-100 parts by weight of chlorinated polyethylene into 0-60 parts by weight of styrene-butadiene-methyl methacrylate copolymer or styrene-butadiene copolymer, adding 0-200 parts by weight of water and 0.1-0.5 part by weight of free radical initiator, and then carrying out polymerization reaction at 50-70 ℃; continuously adding 0.2-2.5 parts by weight of surfactant, 0.1-0.3 part by weight of free radical initiator and 0-40 parts by weight of alkyl acrylate-styrene-acrylonitrile copolymer or alkyl acrylate into the mixture for polymerization reaction to obtain the toughening modifier.
10. A polyvinyl chloride composition comprising 3 to 15 parts by weight of the toughening modifier according to any one of claims 1 to 9, 100 parts by weight of a polyvinyl chloride resin, 0.8 to 3 parts by weight of a stabilizer, 0.5 to 2 parts by weight of a processing aid, 0.2 to 1 part by weight of an internal lubricant and 0.1 to 0.5 part by weight of an external lubricant;
wherein the stabilizer is selected from one or more of organotin stabilizer, calcium zinc stabilizer or lead salt stabilizer.
11. Use of a polyvinyl chloride composition according to claim 10 for toys and packaging materials.
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| CN105854770A (en) * | 2016-06-01 | 2016-08-17 | 山东日科橡塑科技有限公司 | High-efficiency, high-performance and corrosion-resistant metal chlorination reaction kettle |
| CN106349411A (en) * | 2016-09-24 | 2017-01-25 | 山东日科化学股份有限公司 | Toughening modifying agent for transparent polyvinyl chloride product and high-transparency polyvinyl chloride mixture |
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| EP0603753B1 (en) * | 1992-12-23 | 1997-01-22 | The B.F. Goodrich Company | CPVC composition for extrusion of pipe, and pipe therefrom |
| CN102260361B (en) * | 2011-06-03 | 2013-05-22 | 杭州新元化工技术开发有限公司 | Preparation method of chlorinated polyethylene |
| CN107141382B (en) * | 2017-06-30 | 2019-05-10 | 江苏中煦高分子材料有限公司 | A kind of chlorination low molecular weight polyethylene synthesis technology |
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| CN105854770A (en) * | 2016-06-01 | 2016-08-17 | 山东日科橡塑科技有限公司 | High-efficiency, high-performance and corrosion-resistant metal chlorination reaction kettle |
| CN106349411A (en) * | 2016-09-24 | 2017-01-25 | 山东日科化学股份有限公司 | Toughening modifying agent for transparent polyvinyl chloride product and high-transparency polyvinyl chloride mixture |
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