CN115991807B - Yellowing-resistant polyvinyl chloride resin and preparation method thereof - Google Patents
Yellowing-resistant polyvinyl chloride resin and preparation method thereof Download PDFInfo
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- CN115991807B CN115991807B CN202111213303.8A CN202111213303A CN115991807B CN 115991807 B CN115991807 B CN 115991807B CN 202111213303 A CN202111213303 A CN 202111213303A CN 115991807 B CN115991807 B CN 115991807B
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- 238000004383 yellowing Methods 0.000 title claims abstract description 88
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 78
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 77
- 239000011347 resin Substances 0.000 title claims abstract description 53
- 229920005989 resin Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002270 dispersing agent Substances 0.000 claims abstract description 42
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 38
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- 238000006136 alcoholysis reaction Methods 0.000 claims description 29
- 239000013530 defoamer Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 17
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- -1 chloro-2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphite Chemical compound 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 8
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 8
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 7
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical class [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- LXWZXEJDKYWBOW-UHFFFAOYSA-N 2,4-ditert-butyl-6-[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O LXWZXEJDKYWBOW-UHFFFAOYSA-N 0.000 claims description 4
- FCIIEZYZYBGUBJ-UHFFFAOYSA-N 2-ethyl-1-propyl-1-trimethoxysilylhydrazine Chemical compound CCNN(CCC)[Si](OC)(OC)OC FCIIEZYZYBGUBJ-UHFFFAOYSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical group CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 2
- 229920001296 polysiloxane Polymers 0.000 claims 2
- 238000011143 downstream manufacturing Methods 0.000 abstract description 4
- 239000000839 emulsion Substances 0.000 description 34
- 239000000047 product Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 9
- WKEWCYHGACEYTR-UHFFFAOYSA-N tert-butyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(C)(C)C WKEWCYHGACEYTR-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a yellowing-resistant polyvinyl chloride resin and a preparation method thereof, comprising the following steps: s1: vacuumizing a polymerization kettle, adding water, a dispersing agent, a monomer and an initiator into the polymerization kettle, and increasing the temperature of the polymerization kettle to start polymerization reaction; s2: adding a defoaming agent in the reaction process, and adding a composite antioxidant type terminator and a yellowing-resistant auxiliary agent after the reaction is finished; s3: and (3) stripping and drying the slurry in the polymerization kettle to obtain the yellowing-resistant polyvinyl chloride resin. The yellowing-resistant polyvinyl chloride resin and the preparation method thereof provided by the invention can effectively improve the thermal stability, ageing whiteness and yellowing resistance of the polyvinyl chloride resin, and the yellowing problem of products in the downstream processing process is effectively improved.
Description
Technical Field
The invention relates to the field of polyvinyl chloride resin, in particular to yellowing-resistant polyvinyl chloride resin and a preparation method thereof.
Background
Polyvinyl chloride (PVC) resin is polymerized from vinyl chloride monomer, and has been widely used worldwide due to the advantages of excellent mechanical properties, corrosion resistance, low price and the like, and the use amount of the PVC resin is high in various synthetic materials, and the consumption amount of the PVC resin is increased year by year. Along with the continuous development of downstream customers, the requirements on the PVC resin are increasingly increased, such as the requirements on whiteness and yellowing resistance of PVC downstream products, and various auxiliary agents are usually added into the PVC resin by downstream manufacturers in the processing process to improve various properties of PVC products, but along with the expansion of PVC productivity, the PVC downstream is gradually developed into the market of buyers, so that the PVC resin with high whiteness and yellowing resistance is particularly important.
The Chinese patent CN107033374B adopts ethanol, liquid carbolic acid, blue pigment substances, deionized water and other substances to compound a whitening auxiliary agent, and uses the whitening auxiliary agent Bai Chuji to whiten the polyvinyl chloride resin, but the method utilizes the color complementation principle to weaken the visual yellow depth of the resin, so that the whiteness and yellowing resistance of the PVC resin are not improved fundamentally, the resin is easy to degrade at high temperature in the downstream processing process, serious yellowing of the product is caused, the mechanical property is obviously reduced, and the downstream application of the PVC product is greatly limited.
The Chinese patent CN106893011B adopts the diethyl hydroxylamine and the antioxidant to compound the terminator, the whiteness and the thermal stability of the PVC product are improved by using the terminator, the thermal stability of the product is improved to a certain extent by the method, the yellowing of the PVC resin in the downstream high-temperature processing process is weakened, but the antioxidant in the terminator used by the method can oxidize into the color-developing substances such as quinones at high temperature, and meanwhile, the PVC product still can generate relatively rapid yellowing after the antioxidant is consumed along with the increase of the processing temperature of the downstream product and the extension of the processing time.
Aiming at the problems, the problems of low whiteness and poor yellowing resistance of the polyvinyl chloride resin prepared by the existing polyvinyl chloride preparation method are required to be solved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a preparation method of yellowing-resistant polyvinyl chloride resin, which is used for solving the problems of low whiteness and poor yellowing resistance of the polyvinyl chloride resin prepared by the existing polyvinyl chloride preparation method.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for preparing a yellowing-resistant polyvinyl chloride resin, the method comprising the steps of:
s1: vacuumizing a polymerization kettle, adding water, a dispersing agent, a monomer and an initiator into the polymerization kettle, and increasing the temperature of the polymerization kettle to start polymerization reaction;
s2: adding a defoaming agent in the reaction process, and adding a composite antioxidant type terminator and a yellowing-resistant auxiliary agent after the reaction is finished;
s3: the slurry in the polymerization kettle is subjected to steam stripping and drying to prepare the yellowing-resistant polyvinyl chloride resin;
wherein, the yellowing-resistant auxiliary agent in the S2 has the following structure:
according to the invention, the modified vanadium oxide yellowing-resistant auxiliary agent which can be used with the antioxidant type terminator in a synergistic way is added at the later stage of the polymerization reaction, the antioxidant overcomes the defect that the traditional antioxidant is easy to migrate and separate out, in the process of PVC thermal degradation, the hydroperoxide generated by PVC degradation can be decomposed, the quinone colored substance generated by the terminator after oxidation is reduced into phenol (colorless), and meanwhile, hydrogen chloride generated by PVC thermal degradation can be absorbed, and the metal ion of PVC degradation is stably promoted, so that the unstable structure content of PVC in the downstream processing process can be better reduced, the photo/thermal stability, the oxidation resistance and the antibacterial property are improved, and the high whiteness and the yellowing resistance of PVC resin are improved.
In the invention, the mass ratio of the vinyl chloride monomer, the water, the dispersing agent, the initiator, the defoamer, the terminator and the yellowing-resistant auxiliary agent in S1 and S2 is (1100-1300): (2000-2100): (1-2): (0.1-0.5): (1-4): (1-4), preferably (1150-1250): (2000-2050): (2-3): (1-2): (0.2-0.4): (1-2): (1-2), more preferably 1200:2040:2.5:1.6:0.3:1:2.
In the invention, the dispersing agent S1 is compounded by three polyvinyl alcohol dispersing agents with alcoholysis degrees of 88%,72% and 55% respectively; preferably, the mass ratio of the three polyvinyl alcohol dispersants is (1-4): (1-6): (0-4), preferably (1-3): (1-4): (1-2), more preferably the ratio is 2:3:1.
In the invention, the initiator S1 is tert-butyl peroxyneodecanoate and cumyl peroxyneodecanoate.
In the invention, the polymerization reaction temperature of S1 is 55-64 ℃, and the polymerization pressure drop is 0.1-0.2MPa.
In the invention, the defoamer in S2 is a polyether defoamer and/or a polyether modified organosilicon defoamer, preferably a polyether modified organosilicon defoamer.
In the invention, the composite antioxidant terminator in S2 is a plurality of antioxidants 1076, 245, DLTDP and diethylhydroxylamine.
In the invention, the preparation method of the yellowing-resistant auxiliary agent S2 comprises the following steps:
SS1: heating 2, 4-di-tert-butylphenol, water and concentrated sulfuric acid, adding paraformaldehyde, and carrying out suction filtration, washing and drying after the constant-temperature reaction is finished;
SS2: adding 2,2 '-methylenebis (4, 6-di-tert-butylphenol), petroleum ether and triethylamine into a reactor, heating, adding a phosphorus trichloride solution, filtering, washing with water and drying after the constant temperature reaction is finished to obtain chloro-2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphite;
SS3: adding chloro-2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphite and modified vanadium dioxide into a reactor, adding dimethylformamide and potassium carbonate, heating, filtering and drying after the constant temperature reaction is finished, and obtaining white powder which is the target yellowing-resistant auxiliary agent.
In the invention, the preparation method of the modified vanadium oxide of SS3 comprises the following steps:
adding ethanol and water into a reactor, adding glacial acetic acid and N- (2-ethylamino) -3-propylamino trimethoxysilane, adding vanadium oxide dispersion liquid, stirring, centrifuging the reaction liquid after the reaction is finished to obtain a precipitate, cleaning the precipitate, and drying to obtain modified vanadium oxide powder.
Another object of the invention is to provide a yellowing resistant auxiliary.
The yellowing-resistant auxiliary agent is prepared by adopting an auxiliary agent preparation method in the yellowing-resistant polyvinyl chloride resin preparation method.
It is still another object of the present invention to provide a yellowing-resistant polyvinyl chloride resin.
The yellowing-resistant polyvinyl chloride resin is prepared by the preparation method of the yellowing-resistant polyvinyl chloride resin or by the yellowing-resistant auxiliary agent, and the whiteness of the resin is 78-81 after 160 ℃ heat aging and 75-79 after 40min of double-roll open milling at 185 ℃. .
The invention has the following beneficial effects:
the yellowing-resistant polyvinyl chloride resin can reduce unstable structures in molecular chains of the polyvinyl chloride resin, eliminate residual initiator and free radicals, effectively weaken thermal degradation of the resin caused by heating in a downstream processing process, inhibit yellowing of PVC at high temperature, and obviously improve yellowing resistance and thermal stability of a product, wherein the whiteness of the resin after 160 ℃ heat aging is 78-81, and the whiteness of a film after 185 ℃ double-roll open mill is 75-79.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples.
Raw material information:
vinyl chloride (Wanhua chemistry, purity 99.995), deionized water (homemade), alcoholysis degree 88% dispersant solution: (Shanghai day Tet code company, solid content 7%), alcoholysis degree 72% dispersant solution (Shanghai day Tet code company, solid content 7%), alcoholysis degree 55% dispersant solution (Shanghai day Tet code company, solid content 40%), tert-butyl peroxyneodecanoate emulsion (Tianjin Li Anlong, solid content 50%), cumyl peroxyneodecanoate emulsion (Tianjin Li Anlong, solid content 50%), composite terminator emulsion (Basv company, solid content 60%), defoamer (Shanghai Yingzhang company, solid content 50%), 2, 4-di-tert-butylphenol, paraformaldehyde, concentrated sulfuric acid, phosphorus trichloride, triethylamine, petroleum ether, absolute ethyl alcohol, glacial acetic acid, N- (2-ethylamino) -3-propylaminotrimethoxysilane, diethyl hydroxylamine (Beijing enokii, AR), nano vanadium oxide (Beijing enokii company, 100-200 nm)
The characterization method comprises the following steps:
nuclear magnetic analysis: the DRX-400 nuclear magnetic resonance wave-pup meter of Bruce spectrum instrument limited, germany, the working frequency is 400Hz, and TMS is used as an internal standard;
infrared analysis: scanning with a scanning range of 4000-400cm by KBr tabletting using a TENSOP 27 infrared spectrometer from Bruce spectrometer, inc. of Germany -1 Resolution of 0.09cm -1 The number of scans was 32;
aging whiteness test: the Hunterlab Eurolap 16 integrating sphere color difference GB/T15595-2008 test standard is used;
whiteness test of open-loop film: 30g of polyvinyl chloride powder, 0.3g of zinc stearate, 0.3g of barium stearate and 12ml of dioctyl phthalate are weighed, uniformly mixed and then kept stand at room temperature for 5min. The uniformly mixed powder was added to a twin-roll mill (XH-401 CE-160350 model, dongguan tin bloom Co.) preheated to 185 ℃ in advance, the distance between the left and right rolls was 1mm, the speeds of the front and rear rolls were 24rpm and 16rpm, respectively, one piece of polyvinyl chloride film was taken out every 5 minutes of the mill, the total mill was conducted for 40 minutes, and the whiteness value of the polyvinyl chloride film was detected by a haze meter (Hunterlab Co., vista model).
And (3) synthesizing a yellowing-resistant auxiliary agent:
A. 20g of 2, 4-di-tert-butylphenol, 200g of water and 2g of concentrated sulfuric acid (98%) are added into a three-neck flask in sequence, the mixture is heated to 70 ℃,10 g of paraformaldehyde is added, and the mixture is reacted for 8 hours at constant temperature under stirring. After the reaction, the mixture is filtered under reduced pressure while the mixture is hot, and the mixture is washed with hot water at 70 ℃ for 3 times until the filtrate does not foam any more, and is dried at 50 ℃ for 3 hours.
B. 4.24g of 2,2' -methylenebis (4, 6-di-t-butylphenol), 60ml of petroleum ether and 2.20g of triethylamine were charged into a three-necked flask, the temperature was raised to 40℃and 16.84g of a petroleum ether solution (concentration: 10% by weight) of phosphorus trichloride was slowly added dropwise thereto, and the reaction was continued at constant temperature for 6 hours. After the reaction is finished, filtering at room temperature, washing for 3 times, and drying at 50 ℃ for 3 hours to obtain chloro-2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphite.
C. Weighing 4g of nano vanadium oxide, and dispersing in 200ml of absolute ethyl alcohol for 2 hours by ultrasonic treatment for standby. 150ml of absolute ethanol and 15ml of deionized water were added to a three-necked flask, 100. Mu.l of glacial acetic acid was added thereto, 4g of N- (2-ethylamino) -3-propylaminotrimethoxysilane was added dropwise thereto, and the mixture was stirred for 2 hours. And (3) dropwise adding the nano vanadium oxide dispersion liquid into a three-neck flask, stirring at 80 ℃ for 12 hours, centrifuging the reaction liquid to obtain a precipitate, washing the precipitate with absolute ethyl alcohol for 3 times, and vacuum drying for 2 hours to obtain dry powder, namely the modified vanadium oxide.
D. 10g of chloro-2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphite and 5g of modified vanadium dioxide are added into a three-neck flask, 200g of dimethylformamide and 2.5g of potassium carbonate are added, the temperature is raised to 90 ℃ for constant temperature reaction for 4 hours, after the reaction is finished, the mixture is filtered at room temperature and dried at 50 ℃ for 3 hours, and white powder, namely the yellowing-resistant auxiliary agent, is obtained. The infrared and nuclear magnetic analysis results are shown in tables 1 and 2.
Table 1 anti-yellowing auxiliary infrared signature attribution
| Displacement/cm -1 | Attribution to |
| 2955.70 | Methyl stretching vibration peak |
| 1629.35 | Secondary amino stretching vibration peak |
| 1471.07 | Vibration peak of aromatic ring skeleton |
| 1407.58，1362.99 | Characteristic peaks of t-butyl |
| 1107.20 | Characteristic peak of siloxyl group |
| 828.43 | Characteristic peak of benzene ring substitution |
| 450.56 | Characteristic peak of vanadium oxide |
TABLE 2 anti-yellowing auxiliary Nuclear magnetic Spectrometry peak assignment
| Chemical shift/ppm | Attribution to | Atomic number |
| 1.20-1.35 | Methyl hydrogen | 36 |
| 1.98-2.03 | Para-amino hydrogen | 2 |
| 3.21-3.51 | Methylene hydrogen | 12 |
| 6.7-7.2 | Benzene ring hydrogen | 10 |
Example 1
The 5L reactor was subjected to three vacuum operations, each time to a reactor pressure of-0.1 MPaG, 1100g of vinyl chloride monomer, 2100g of deionized water, 14.28g of a 88% alcoholysis degree dispersant solution, 21.4g of a 72% alcoholysis degree dispersant solution, 1.25g of a 55% alcoholysis degree dispersant solution, 0.5g of a cumyl peroxyneodecanoate emulsion, and 1.5g of a tert-butyl peroxydecanoate emulsion were added to the reactor, and the temperature of the reactor was raised to 55℃to initiate polymerization. Observing the pressure drop of the system in the reaction process, adding 0.2g of defoamer emulsion after the reaction is carried out for 2.5 hours, adding 1.67g of composite terminator emulsion and 1g of yellowing-resistant auxiliary agent (phosphite grafted vanadium dioxide) when the pressure drop of the system reaches 0.15MPa, removing the pressure of the reaction kettle, stripping the slurry at 80 ℃ for 1 hour, filtering at room temperature, and drying PVC powder at 50 ℃ for 2 hours to obtain the yellowing-resistant polyvinyl chloride resin.
Example 2
The 5L reactor was subjected to three vacuum operations, each time to a reactor pressure of-0.1 MPaG, 1300g of vinyl chloride monomer, 2000g of deionized water, 9.52g of a 88% alcoholysis degree dispersant solution, 14.28g of a 72% alcoholysis degree dispersant solution, 0.83g of a 55% alcoholysis degree dispersant solution, 1.0g of a cumyl peroxyneodecanoate emulsion, and 3.0g of a tert-butyl peroxydecanoate emulsion were added to the reactor, and the temperature of the reactor was raised to 64℃to initiate polymerization. Observing the pressure drop of the system in the reaction process, adding 1g of defoamer emulsion after the reaction is carried out for 2.5 hours, adding 6.67g of composite terminator emulsion and 4g of yellowing-resistant auxiliary agent (phosphite grafted vanadium dioxide) when the pressure drop of the system reaches 0.15MPa, discharging the pressure of the reaction kettle, stripping the slurry at 80 ℃ for 1 hour, filtering at room temperature, and drying PVC powder at 50 ℃ for 2 hours to obtain the yellowing-resistant polyvinyl chloride resin.
Example 3
The 5L reactor was subjected to three vacuum operations, each time to a reactor pressure of-0.1 MPaG, 1200g of vinyl chloride monomer, 2040g of deionized water, 11.90g of an 88% alcoholysis degree dispersant solution, 17.85g of a 72% alcoholysis degree dispersant solution, 1.04g of a 55% alcoholysis degree dispersant solution, 0.8g of a cumyl peroxyneodecanoate emulsion, and 2.4g of a tert-butyl peroxydecanoate emulsion were added to the reactor, and the temperature of the reactor was raised to 56.8℃to initiate polymerization. Observing the pressure drop of the system in the reaction process, adding 0.6g of defoamer emulsion after the reaction is carried out for 2.5 hours, adding 3.33g of composite terminator emulsion and 2g of yellowing-resistant auxiliary agent (phosphite grafted vanadium dioxide) when the pressure drop of the system reaches 0.15MPa, removing the pressure of the reaction kettle, stripping the slurry at 80 ℃ for 1 hour, filtering at room temperature, and drying PVC powder at 50 ℃ for 2 hours to obtain the yellowing-resistant polyvinyl chloride resin.
Example 4
The 5L reactor was subjected to three vacuum operations, each time to a reactor pressure of-0.1 MPaG, 1200g of vinyl chloride monomer, 2040g of deionized water, 11.90g of an 88% alcoholysis degree dispersant solution, 17.85g of a 72% alcoholysis degree dispersant solution, 1.04g of a 55% alcoholysis degree dispersant solution, 0.8g of a cumyl peroxyneodecanoate emulsion, and 2.4g of a tert-butyl peroxydecanoate emulsion were added to the reactor, and the temperature of the reactor was raised to 56.8℃to initiate polymerization. Observing the pressure drop of the system in the reaction process, adding 0.6g of defoamer emulsion after the reaction is carried out for 2.5 hours, adding 1.67g of composite terminator emulsion and 2g of yellowing-resistant auxiliary agent (phosphite grafted vanadium dioxide) when the pressure drop of the system reaches 0.15MPa, removing the pressure of the reaction kettle, stripping the slurry at 80 ℃ for 1 hour, filtering at room temperature, and drying PVC powder at 50 ℃ for 2 hours to obtain the yellowing-resistant polyvinyl chloride resin.
Example 5
The 5L reactor was subjected to three vacuum operations, each time to a reactor pressure of-0.1 MPaG, 1200g of vinyl chloride monomer, 2040g of deionized water, 11.90g of an 88% alcoholysis degree dispersant solution, 17.85g of a 72% alcoholysis degree dispersant solution, 1.04g of a 55% alcoholysis degree dispersant solution, 0.8g of a cumyl peroxyneodecanoate emulsion, and 2.4g of a tert-butyl peroxydecanoate emulsion were added to the reactor, and the temperature of the reactor was raised to 56.8℃to initiate polymerization. Observing the pressure drop of the system in the reaction process, adding 0.6g of defoamer emulsion after the reaction is carried out for 2.5 hours, adding 1.67g of composite terminator emulsion and 3g of yellowing-resistant auxiliary agent (phosphite grafted vanadium dioxide) when the pressure drop of the system reaches 0.15MPa, removing the pressure of the reaction kettle, stripping the slurry at 80 ℃ for 1 hour, filtering at room temperature, and drying PVC powder at 50 ℃ for 2 hours to obtain the yellowing-resistant polyvinyl chloride resin.
Example 6
The 5L reactor was subjected to three vacuum operations, each time to a reactor pressure of-0.1 MPaG, 1200g of vinyl chloride monomer, 2040g of deionized water, 11.90g of an 88% alcoholysis degree dispersant solution, 17.85g of a 72% alcoholysis degree dispersant solution, 1.04g of a 55% alcoholysis degree dispersant solution, 0.8g of a cumyl peroxyneodecanoate emulsion, and 2.4g of a tert-butyl peroxydecanoate emulsion were added to the reactor, and the temperature of the reactor was raised to 56.8℃to initiate polymerization. Observing the pressure drop of the system in the reaction process, adding 0.6g of defoamer emulsion after the reaction is carried out for 2.5 hours, adding 3.33g of composite terminator emulsion and 3g of yellowing-resistant auxiliary agent (phosphite grafted vanadium dioxide) when the pressure drop of the system reaches 0.15MPa, removing the pressure of the reaction kettle, stripping the slurry at 80 ℃ for 1 hour, filtering at room temperature, and drying PVC powder at 50 ℃ for 2 hours to obtain the yellowing-resistant polyvinyl chloride resin.
Comparative example 1
This comparative example is compared to example 4, except that no yellowing resistance promoter phosphite grafted vanadium dioxide is added.
The 5L reactor was subjected to three vacuum operations, each time to a reactor pressure of-0.1 MPaG, 1200g of vinyl chloride monomer, 2040g of deionized water, 11.90g of an 88% alcoholysis degree dispersant solution, 17.85g of a 72% alcoholysis degree dispersant solution, 1.04g of a 55% alcoholysis degree dispersant solution, 0.8g of a cumyl peroxyneodecanoate emulsion, and 2.4g of a tert-butyl peroxydecanoate emulsion were added to the reactor, and the temperature of the reactor was raised to 56.8℃to initiate polymerization. Observing the pressure drop of the system in the reaction process, adding 0.6g of defoamer emulsion after the reaction is carried out for 2.5 hours, adding 1.67g of composite terminator emulsion when the pressure drop of the system reaches 0.15MPa, removing the pressure of the reaction kettle, stripping the slurry at 80 ℃ for 1 hour, filtering at room temperature, and drying PVC powder at 50 ℃ for 2 hours to obtain the polyvinyl chloride resin.
Comparative example 2
This comparative example is compared to example 3, except that no terminator was added.
The 5L reactor was subjected to three vacuum operations, each time to a reactor pressure of-0.1 MPaG, 1200g of vinyl chloride monomer, 2040g of deionized water, 11.90g of an 88% alcoholysis degree dispersant solution, 17.85g of a 72% alcoholysis degree dispersant solution, 1.04g of a 55% alcoholysis degree dispersant solution, 0.8g of a cumyl peroxyneodecanoate emulsion, and 2.4g of a tert-butyl peroxydecanoate emulsion were added to the reactor, and the temperature of the reactor was raised to 56.8℃to initiate polymerization. Observing the pressure drop of the reaction process, adding 0.6g of defoamer emulsion after the reaction is carried out for 2.5 hours, adding 1g of diethylhydroxylamine when the pressure drop of the system reaches 0.15MPa, removing the pressure of the reaction kettle by 2g of yellowing-resistant auxiliary agent, stripping the slurry for 1 hour at 80 ℃, filtering at room temperature, and drying PVC powder for 2 hours at 50 ℃ to obtain the polyvinyl chloride resin.
The polyvinyl chloride powder obtained under different production conditions is subjected to heat aging whiteness and dynamic heat stability test, and the test results are as follows:
TABLE 3 results of ageing whiteness and dynamic thermal stability test of finished PVC
As can be seen from Table 3, the yellowing-resistant polyvinyl chloride resins prepared in examples 1 to 6 show excellent heat aging whiteness and yellowing resistance, the aging whiteness value at 160 ℃ can reach 78 to 81, and the whiteness of an open-roll film product after open-roll milling at 185 ℃ for 40min can reach 75 to 79. Comparing examples 1-6, it can be found that, by increasing the dosage of the composite terminator and the yellowing-resistant auxiliary agent and adjusting the ratio of the composite terminator to the yellowing-resistant auxiliary agent in the same proportion, the whiteness and the yellowing-resistant performance of the product can be improved, and the effect of adjusting the ratio of the composite terminator to the yellowing-resistant auxiliary agent is stronger, mainly because the antioxidant component in the terminator is oxidized and discolored by itself after being heated, if the dosage is too much, part of the antioxidant is oxidized by itself to reduce the whiteness of PVC powder, more yellowing-resistant auxiliary agent is needed to assist the antioxidant to play a role, so that when the ratio of the composite terminator to the yellowing-resistant auxiliary agent is adjusted to about 1:2, good synergistic effect can be exerted between the two, thereby improving the heat aging whiteness of the PVC resin. In addition, as compared with comparative example 1, it was found that if only the composite terminator is used, the yellowing-resistant auxiliary is not used, the aged whiteness and yellowing resistance of the product are significantly reduced, because the yellowing-resistant auxiliary can form a synergistic effect with the terminator, the antioxidant component after reduction and oxidation reduces the formation of unstable structures in PVC molecular chains and the removal of hydrogen chloride, chelate metal ions, and the product has good water resistance, cohesiveness, antibacterial property and extraction resistance, is more favorable for the terminator to exert the yellowing-resistant effect, and reduces the discoloration of the product caused by the oxidation of the terminator itself. As can be seen from comparative examples 4 and 2, if the compound terminator is not used, but the diethylhydroxylamine single component terminator is used in combination with the yellowing-resistant auxiliary agent, the aged whiteness value and the yellowing-resistant performance of the product still cannot be effectively improved, because the diethylhydroxylamine only has the function of terminating free radicals, the heat stability and the ageing-resistant performance of the product cannot be effectively improved, and the synergistic effect with the yellowing-resistant auxiliary agent cannot be formed.
According to the embodiment and the comparative example, compared with the traditional polyvinyl chloride preparation method, the polyvinyl chloride resin prepared by the preparation method of the yellowing-resistant polyvinyl chloride resin provided by the invention has higher heat aging whiteness, better yellowing resistance, and greatly improves the application performance of the polyvinyl chloride resin in the fields of super-permeable films, floor film layers and the like.
Claims (14)
1. A method for preparing yellowing-resistant polyvinyl chloride resin, which is characterized by comprising the following steps:
s1: vacuumizing a polymerization kettle, adding water, a dispersing agent, vinyl chloride monomer and an initiator into the polymerization kettle, and raising the temperature of the polymerization kettle to start polymerization reaction;
s2: adding a defoaming agent in the reaction process, and adding a composite antioxidant type terminator and a yellowing-resistant auxiliary agent after the reaction is finished;
s3: the slurry in the polymerization kettle is subjected to steam stripping and drying to prepare the yellowing-resistant polyvinyl chloride resin;
wherein, the yellowing-resistant auxiliary agent in the S2 has the following structure:
2. the preparation method according to claim 1, wherein the mass ratio of the vinyl chloride monomer, water, dispersant, initiator, defoamer, terminator and yellowing-resistant auxiliary agent of S1 and S2 is (1100-1300): (2000-2100): (2-3): (1-2): (0.1-0.5): (1-4): (1-4).
3. The preparation method according to claim 2, wherein the mass ratio of the vinyl chloride monomer, water, dispersant, initiator, defoamer, terminator and yellowing-resistant auxiliary agent of S1 and S2 is (1150-1250): (2000-2050): (2-3): (1-2): (0.2-0.4): (1-2): (1-2).
4. The preparation method according to claim 3, wherein the mass ratio of the vinyl chloride monomer, water, dispersant, initiator, defoamer, terminator and yellowing-resistant auxiliary agent in S1 and S2 is 1200:2040:2.5:1.6:0.3:1:2.
5. The preparation method according to claim 1 or 2, wherein the dispersant S1 is compounded by three polyvinyl alcohol dispersants with alcoholysis degree of 88%,72% and 55% respectively;
and/or S1, wherein the initiator is tert-butyl peroxyneodecanoate and cumyl peroxyneodecanoate;
and/or the polymerization temperature of S1 is 55-64 ℃ and the polymerization pressure drop is 0.1-0.2MPa.
6. The preparation method according to claim 5, wherein the mass ratio of the three polyvinyl alcohol dispersants is (1-4): 1-6): 0-4.
7. The preparation method according to claim 6, wherein the mass ratio of the three polyvinyl alcohol dispersants is (1-3): 1-4): 1-2.
8. The preparation method according to claim 7, wherein the mass ratio of the three polyvinyl alcohol dispersants is 2:3:1.
9. The preparation method according to claim 1, wherein the defoamer of S2 is a polyether defoamer and/or a polyether modified silicone defoamer;
and/or the composite antioxidant terminator in S2 is a plurality of antioxidants 1076, 245, DLTDP and diethylhydroxylamine.
10. The method of claim 9, wherein S2 said defoamer is a polyether modified silicone defoamer.
11. The preparation method of the yellowing resistance additive according to claim 1, wherein the preparation method of the yellowing resistance additive of S2 comprises the following steps:
SS1: heating 2, 4-di-tert-butylphenol, water and concentrated sulfuric acid, adding paraformaldehyde, and performing suction filtration, washing and drying after the constant-temperature reaction is finished to obtain 2,2' -methylenebis (4, 6-di-tert-butylphenol);
SS2: adding 2,2 '-methylenebis (4, 6-di-tert-butylphenol), petroleum ether and triethylamine into a reactor, heating, adding a phosphorus trichloride solution, filtering, washing with water and drying after the constant temperature reaction is finished to obtain chloro-2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphite;
SS3: adding chloro-2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphite and modified vanadium dioxide into a reactor, adding dimethylformamide and potassium carbonate, heating, filtering and drying after the constant temperature reaction is finished, and obtaining white powder which is the target yellowing-resistant auxiliary agent.
12. The method of claim 11, wherein the method of preparing the modified vanadium dioxide of SS3 comprises:
adding ethanol and water into a reactor, adding glacial acetic acid and N- (2-ethylamino) -3-propylamino trimethoxysilane, adding vanadium dioxide dispersion liquid, stirring, centrifuging the reaction liquid after the reaction is finished to obtain a precipitate, cleaning the precipitate, and drying to obtain modified vanadium dioxide powder.
13. The yellowing-resistant auxiliary agent is prepared by adopting the yellowing-resistant auxiliary agent preparation method in the yellowing-resistant polyvinyl chloride resin preparation method according to claim 11 or 12.
14. A yellowing-resistant polyvinyl chloride resin prepared by the preparation method of the yellowing-resistant polyvinyl chloride resin of any one of claims 1 to 12 or by the yellowing-resistant auxiliary agent of claim 13, wherein the whiteness of the resin after 160 ℃ heat aging is 78 to 81, and the whiteness of a film after 185 ℃ two-roll open mill is 75 to 79 after 40 minutes.
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| WO2013107080A1 (en) * | 2012-01-19 | 2013-07-25 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide powdery slurry and preparation process thereof |
| JP2017222806A (en) * | 2016-06-17 | 2017-12-21 | コニカミノルタ株式会社 | Method for producing thermochromic film |
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| WO2013107080A1 (en) * | 2012-01-19 | 2013-07-25 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide powdery slurry and preparation process thereof |
| JP2017222806A (en) * | 2016-06-17 | 2017-12-21 | コニカミノルタ株式会社 | Method for producing thermochromic film |
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| Title |
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| 一种新型醌亚胺化合物的合成、表征及应用;崔金海;张淑芬;张予东;;化工进展;36(10);第3850-3859页 * |
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