CN1274726C - Polyvinyl alcohol with high degree of polymerization and its preparing process - Google Patents
Polyvinyl alcohol with high degree of polymerization and its preparing process Download PDFInfo
- Publication number
- CN1274726C CN1274726C CN 03135392 CN03135392A CN1274726C CN 1274726 C CN1274726 C CN 1274726C CN 03135392 CN03135392 CN 03135392 CN 03135392 A CN03135392 A CN 03135392A CN 1274726 C CN1274726 C CN 1274726C
- Authority
- CN
- China
- Prior art keywords
- polymerization
- polyvinyl alcohol
- degree
- alcoholysis
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 66
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 54
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title abstract description 22
- 230000008569 process Effects 0.000 title abstract description 8
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 28
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 15
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000008234 soft water Substances 0.000 claims description 22
- -1 alkali metal salt Chemical class 0.000 claims description 15
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002612 dispersion medium Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 5
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical group CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- PLZZPPHAMDJOSR-UHFFFAOYSA-N nonanenitrile Chemical compound CCCCCCCCC#N PLZZPPHAMDJOSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 238000005502 peroxidation Methods 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical group CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims 2
- 239000005056 polyisocyanate Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000010558 suspension polymerization method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明是一种高聚合度的聚乙烯醇及其合成工艺。本发明的工艺采用悬浮聚合方式，用自由基低温引发体系，在10～60℃下，经过2～10小时的聚合得到高聚合度的聚乙酸乙烯酯，并对该聚乙酸乙烯酯进行醇解反应，获得高聚合度的聚乙烯醇。本发明的合成工艺，具有反应温度适宜、工艺控制简单、聚合转化率高、聚合时间短、产物纯度高、易于工业化等特点。本发明的高聚合度聚乙烯醇的聚合度在5000以上，最佳为6000-8000，分散度在1.5～2.8，最佳为1.8～2.5，除特别适合于生产高强高模PVA纤维(强度大于20g/d)外，还可用于加工PVA膜、PVA板材、制模件(如喷头和转动部件)以及轮胎芯等。The invention relates to polyvinyl alcohol with a high degree of polymerization and its synthesis process. The process of the present invention adopts a suspension polymerization method, uses a free radical low-temperature initiation system, and obtains polyvinyl acetate with a high degree of polymerization after 2 to 10 hours of polymerization at 10 to 60 ° C, and performs alcoholysis on the polyvinyl acetate reaction to obtain polyvinyl alcohol with a high degree of polymerization. The synthesis process of the present invention has the characteristics of suitable reaction temperature, simple process control, high polymerization conversion rate, short polymerization time, high product purity, easy industrialization and the like. The degree of polymerization of the high degree of polymerization polyvinyl alcohol of the present invention is more than 5000, the best is 6000-8000, the degree of dispersion is 1.5～2.8, the best is 1.8～2.5, except that it is particularly suitable for producing high-strength and high-modulus PVA fibers (intensity greater than 20g/d), it can also be used to process PVA film, PVA sheet, molding parts (such as nozzles and rotating parts) and tire cores.
Description
Technical field
The present invention is the polyvinyl alcohol that obtains a kind of high-polymerization degree with suspension polymerization.
Technical background
Polyvinyl alcohol (PVA) is a kind of excellent property, broad-spectrum polymkeric substance.Its main preparation methods has solution polymerization, mass polymerization, letex polymerization and suspension polymerization.And adopt polyvinyl alcohol of high degree of polymerization to prepare high-strength high-modulus fibre, and can reduce the molecule chain end defective, improve draw ratio, shorten the technological process of production, reduce production costs, the PVA fibre strength of acquisition can reach 20g/d, excellent property.In addition, polyvinyl alcohol of high degree of polymerization can also be used to produce multiple products such as PVA film, PVA sheet material, molding part (as shower nozzle and rotatable parts) and tire core.
The polymerization process of present industrial polyvinyl alcohol is to adopt solution polymerization, the polyvinyl alcohol of acquisition, and the polymerization degree is the highest to be no more than 3000.High-strength high-modulus fibre intensity prepared therefrom is no more than 13g/d.
Mass polymerization is difficult to realize industrialization because polymeric reaction condition is wayward, though the product polymerization degree that obtains is very high, because its degree of branching is also very high, application is restricted.
What the synthetic-highly polymerized degree polyvinyl alcohol of a large amount of patents reports adopted is that method of emulsion polymerization is carried out, as: 1. EP255137,3/1988; 2. the spy opens clear 63,37106/1988; 3. US 4818787/1986; 4. US 4818788/1987; 5. JP 05117307 A2/1993; 6. EP 460502 A2/1991.
In the above-mentioned document, EP255137,3/1988 is disclosed in the emulsion that contains nonionic, anionic emulsifier, superoxide, polyvalent metal ion, selective reduction agent vinyl acetate is carried out polymerization, and after saponification can obtain polyvinyl alcohol of high degree of polymerization.But problems such as this method exists, and operation easier is big, polymerization stability is poor, aftertreatment complexity, wastewater treatment capacity are big, remaining emulsifying agent causes the product poor electrical performance in the polyvinyl alcohol of acquisition, and application is restricted.
The spy opens clear 63,37106/1988 report adopts the method for low temperature emulsion polymerization prepared high-polymerization degree polyvinyl ester, make initiator with redox systems such as ferrous sulfate-rongalite, this method polymerization temperature low (at-60～-15 ℃), wayward, washing difficulty, the polyvinyl alcohol viscosity of acquisition be more than 10000, even be higher than 30000.Metal ion such as iron content, sodium in the product, purity difference, application is restricted.US 4818787/1986 and US4818788/1987 report is with the method for emulsion polymerization prepared high-polymerization degree, and the polyvinyl alcohol limiting viscosity of acquisition even is higher than 3.2dl/g more than 1.5dl/g.Its polymerization degree is about more than 10000, even surpasses 20000.Because the product polymerization degree is too high, the dissolving difficulty, the solution spinning property is poor, is not suitable for fiber sprinning and uses.
Up to now, adopt suspension polymerization synthesizing polyethylene alcohol, some researchs and patent report arranged:
The spy opens clear 61-148209/1986 and has disclosed a kind of method with the suspension polymerization polyvinyl alcohol of high degree of polymerization, and this method polymerization temperature is below 20 ℃, and polymerization velocity is slow, and polymerization time long (above 48 hours) is difficult to realize industrialization.The polyvinyl alcohol limiting viscosity that obtains is more than the 1.5dl/g, and the polymerization degree is more than 10000, and not mentioned product performance and purposes.
EP 250607,7/1988 has disclosed a kind of method with the suspension polymerization polyvinyl alcohol of high degree of polymerization, but the polymerization degree of the polyvinyl alcohol of this method preparation only is 1700, and this method does not have industrialized value.
" Process Technology of Polymer " (day), 44 (9) P409-413,1995; Pollimo (" polymkeric substance "), 20 (6), 1004-1013 (Korea Spro) 1996; Colloid Polym.Sci., (" colloidal state polymer science ") 276 (11), 951-959,1998; J.KoreaFiber Soc., (" Korea S fiber association magazine ") 36 (5), 354-360,1999 reports adopt suspension polymerizations to prepare polyvinyl alcohol or polymerization time is oversize, rate of polymerization too slow (polymerization time more than 47 hours, even want more than 100 hour); Or the polymerization degree is low, and transformation efficiency is not high, all is difficult to realize industrialization.The polymerization degree of the polyvinyl alcohol that obtains is no more than 6000, if be used to produce high-strength high-modulus fibre, the PVA fiber of acquisition is no more than 13g/d by force.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts suspension polymerization, be suitable for the polyvinyl alcohol and the synthesis technique thereof of suitability for industrialized production high-polymerization degree.
The polyvinyl alcohol polymerization degree that this synthesis technique obtains is more than 5000, the best is 6000～8000, dispersity is at 1.5-2.8, the best is 1.8-2.5, is suitable for products such as production high strength high modulus PVA fiber (intensity is greater than 20g/d), PVA film, PVA sheet material, molding part (as shower nozzle and rotatable parts) and tire core.
Its main processes can be expressed as follows:
Monomer preparation → suspension polymerization → separation → alcoholysis → product
The polymerization temperature of suspension polymerization of the present invention is 10～60 ℃, and the best is 20～50 ℃, polymerization time 2～10 hours, and the best is 4～8 hours.
Suspension polymerization system of the present invention is made up of dispersion medium, monomer, dispersion agent, initiator, and its weight percentage is as follows respectively: dispersion medium 40～80%, the best are 50～70%; Monomer 20～60%, the best are 30～50%; Dispersion medium/monomeric mass ratio is between 2: 1～1: 1; Dispersion agent 0～5%, the best are 0.02～2%, initiator 0～4%, and the best is 0.02～2%.
Dispersion medium of the present invention is a soft water; Monomer is a vinyl-acetic ester; Dispersion agent is that the vinyl-acetic ester molar content is 0～40% vinyl alcohol-vinyl acetate copolymer, polyacrylic acid an alkali metal salt, acrylic or methacrylic acid or toxilic acid and multipolymer, gelatin, carboxymethyl cellulose, Natvosol and the composition thereof of vinylbenzene or acrylate or methacrylic ester; Initiator is benzoyl peroxide, dilauroyl peroxide, peroxidation trimethylacetic acid tertiary butyl, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, acetyl peroxide hexanaphthene sulphonyl, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo two different pelargonitrile and combinations thereof.
0～60 ℃ of the temperature of reaction of alcoholysis reaction of the present invention, the best are 20～40 ℃, and in 0.1～2 hour reaction times, the best is 0.4～1.5 hour.
Alcoholysis liquid of the present invention is made up of the polyvinyl acetate of methyl alcohol, sodium hydroxide, soft water and above-mentioned polymerization gained.The weight percentage of alcoholysis liquid is as follows respectively: polyvinyl acetate 2～30%, the best are 4～25%; Methyl alcohol 65～97%, the best are 60～95%; Sodium hydroxide 1～7%, the best are 1.5～6%; Soft water 0～15%, the best are 0.2～10%.
The present invention has following advantage:
1, the polyvinyl alcohol polymerization degree of the present invention's acquisition is more than 5000, and the best is 6000-8000, and dispersity is low, and the linear lag is good.
2, polymerization time of the present invention is short, speed is fast, only is 2～10 hours, and the transformation efficiency height can reach 50%, and synthesis technique is simple, easy to operate, is suitable for industrialization.
3, the polyvinyl alcohol of high degree of polymerization of the present invention's acquisition also can be used for the production of PVA film, PVA sheet material, molding part such as shower nozzle and rotatable parts and ratch tire core etc., broad market prospect except that being particularly suitable for spinning the high strength high modulus PVA fiber.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further detailed; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1:
In reactor, feed nitrogen, add 56.1 parts of soft water, and with 42.5 parts of vinyl-acetic esters, 1 part of gelatin, 0.2 part of Diisopropyl azodicarboxylate and 0.2 part of azo two different pelargonitriles adding reactor, temperature is controlled at 38 ℃, polyreaction 4 hours, the polyvinyl acetate that above-mentioned reaction is obtained is dissolved in 79.5 parts of methyl alcohol, 0.5 part of soft water again, be made into 20% solution, under 30 ℃ of temperature, the sodium hydroxide alcoholysis of adding 1.5% 30 minutes gets white polyethylene powder alcohol product, and its polymerization degree is 6200, alcoholysis degree 99.8%, dispersity 2.41.
Comparative Examples 1: press operation and the condition of embodiment 1, temperature becomes 65 ℃ when being polymerization, and the polymerization degree of the PVA that obtains is 4800, and dispersity is 5.10.
Embodiment 2:
In reactor, feed nitrogen, add 58.6 parts of soft water, and 40 parts of vinyl-acetic esters, 0.4 part of Diisopropyl azodicarboxylate and 1 part of Natvosol are added reactor.Temperature is controlled at 40 ℃, polyreaction 3 hours, the polyvinyl acetate that above-mentioned reaction is obtained is dissolved in 78.5 parts of methyl alcohol, 3.5 parts of soft water again, be made into 18% solution, under 30 ℃ of temperature, add 2.5% sodium hydroxide alcoholysis 35 minutes, get white polyethylene powder alcohol product, its polymerization degree is 7000, alcoholysis degree 99.9%, dispersity 2.30.
Comparative Examples 2: press operation and the condition of embodiment 2, only the consumption with the initiator Diisopropyl azodicarboxylate becomes 4.1%, and then reaction is violent during polymerization, and wayward, the PVA polymerization degree that obtains is 4200, and dispersity is 4.50.
Embodiment 3:
In reactor, feed nitrogen; add 61 parts of soft water; 38 parts of vinyl-acetic esters, 0.2 part Diisopropyl azodicarboxylate, 0.3 part of acetyl peroxide hexanaphthene sulphonyl and 0.5 part of vinyl alcohol-vinyl acetate copolymer are added reactor; temperature is controlled at 30 ℃; polyreaction 3 hours; the polyvinyl acetate that above-mentioned reaction is obtained is dissolved in 80 parts of methyl alcohol, 5 parts of soft water again; be made into 15% solution; under 20 ℃ of temperature; add 3% sodium hydroxide alcoholysis 80 minutes, get white polyethylene powder alcohol product, its polymerization degree is 6000; alcoholysis degree 99.8%, dispersity 1.80.
Comparative Examples 3: press operation and the condition of embodiment 3, only polymerization time is extended to 11 hours, though the polymerization yield increases, the PVA polymerization degree that obtains is 4200, dispersity 3.83.
Embodiment 4:
In reactor, feed nitrogen, add 42.1 parts of soft water, and with 52.7 parts of vinyl-acetic esters, 2.5 part vinyl alcohol-vinyl acetate copolymer, 1 part of acrylic acid and acrylic ester copolymers, 0.5 part polyacrylic acid an alkali metal salt, 0.6 part Diisopropyl azodicarboxylate, 0.3 part azo two different pelargonitriles and 0.3 part of benzoyl peroxide add reactor, temperature is controlled at 15 ℃, polyreaction 10 hours, the polyvinyl acetate that above-mentioned reaction is obtained is dissolved in 88 parts of methyl alcohol again, 6.0 in part soft water, be made into 6% solution, under 55 ℃ of temperature, the sodium hydroxide alcoholysis of adding 3.8% 25 minutes, get white polyethylene powder alcohol product, its polymerization degree is 8000, alcoholysis degree 99.7%, dispersity 1.50.
Embodiment 5:
In reactor, feed nitrogen, add 55 parts of soft water, and with 43.6 parts of vinyl-acetic esters, 1.0 parts of vinylformic acid-Sipacril 2739OFs, 0.2 part of di-cyclohexylperoxy dicarbonate and 0.2 part of benzoyl peroxide adding reactor, temperature is controlled at 25 ℃, reacted 5 hours, the polyvinyl acetate that above-mentioned reaction is obtained is dissolved in 85 parts of methyl alcohol, 3 parts of soft water again, be made into 12% solution, under 40 ℃ of temperature, add 5% sodium hydroxide alkali alcoholysis 30 minutes, get white polyethylene powder alcohol product, its polymerization degree is 7500, alcoholysis degree 99.8%, dispersity 1.80.
Comparative Examples 4: operation and condition by example 4, the alcoholysis time is shortened to 5 minutes, then the alcoholysis degree of gained PVA only is 80%.
Embodiment 6:
In reactor, feed nitrogen, add 64.4 parts of soft water, and with 35 parts of vinyl-acetic esters, 0.1 part of Natvosol, 0.3 part of 2,2'-Azobis(2,4-dimethylvaleronitrile) and 0.2 part of dilauroyl peroxide adding reactor, temperature is controlled at 20 ℃, polyreaction 6.5 hours, the polyvinyl acetate that above-mentioned reaction is obtained is dissolved in 65 parts of methyl alcohol, 1 part of soft water again, be made into 35% solution, add 2.0% sodium hydroxide alcoholysis 60 minutes at 25 ℃, get white polyethylene powder alcohol product, its polymerization degree is 6500, alcoholysis degree 99.9%, dispersity 2.25.
Embodiment 7:
In reactor, feed nitrogen, add 72.5 parts of soft water, and with 26.8 parts of vinyl-acetic esters, 0.04 part of vinyl alcohol-vinyl acetate copolymer, 0.01 part of azo two different pelargonitrile and 0.02 part of benzoyl peroxide adding reactor, temperature is controlled at 55 ℃, polyreaction 2.5 hours, again the polyvinyl acetate that above-mentioned reaction is obtained be dissolved in 89 parts of methyl alcohol, 7 parts of soft water, be made into 4% solution, add 6.8% sodium hydroxide alcoholysis 100 minutes at 15 ℃, get white polyethylene powder alcohol product, its polymerization degree is 8300, alcoholysis degree 99.9%, dispersity 2.80.
Embodiment 8:
In reactor, feed nitrogen, add 50 parts of soft water, and with 40 parts of vinyl-acetic esters, 0.8 part of Walocel MT 20.000PV, 0.01 part of 2,2'-Azobis(2,4-dimethylvaleronitrile) and 0.02 part of benzoyl peroxide adding reactor, temperature is controlled at 45 ℃, polyreaction 5.5 hours, again the polyvinyl acetate that above-mentioned reaction is obtained be dissolved in 69 parts of methyl alcohol, 7.0 parts of soft water, be made into 24% solution, add 6.0% sodium hydroxide alcoholysis 60 minutes at 20 ℃, get white polyethylene powder alcohol product, its polymerization degree is 5000, alcoholysis degree 99.8%, dispersity 2.70.
Claims (4)
1, a kind of polyvinyl alcohol synthetic method is characterized in that: synthetic by following steps:
(1) vinyl acetate polyisocyanate polyaddition: adopt suspension polymerization to carry out the vinyl acetate polyisocyanate polyaddition, 10～60 ℃ of polymerization temperatures, polymerization time 2～10 hours;
(2) alcoholysis: polyvinyl acetate is carried out alcoholysis reaction, obtain polyvinyl alcohol, the polymerization degree of polyvinyl alcohol is 5000
More than;
Wherein, polymerization system and composed as follows:
The polymerization system of described suspension polymerization is made up of dispersion medium, monomer, dispersion agent, initiator, and its weight percentage is as follows respectively: dispersion medium 40～80%, monomer 20～60%, dispersion agent 0～5%, initiator 0～4%; Its dispersion medium is a soft water, monomer is a vinyl-acetic ester, and dispersion agent is that the vinyl-acetic ester molar content is 0～40% vinyl alcohol-vinyl acetate copolymer, polyacrylic acid an alkali metal salt, acrylic or methacrylic acid or toxilic acid and multipolymer, gelatin, carboxymethyl cellulose or Natvosol and the combination thereof of vinylbenzene or acrylate or methacrylic ester; Initiator is benzoyl peroxide, dilauroyl peroxide, peroxidation trimethylacetic acid tertiary butyl, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, acetyl peroxide hexanaphthene sulphonyl, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo two different pelargonitrile and combinations thereof;
Above-mentioned alcoholysis mode and condition:
0～60 ℃ of described alcoholysis reaction temperature, 0.1～2 hour reaction times; Alcoholysis liquid is made up of the polyvinyl acetate of methyl alcohol, sodium hydroxide, soft water and above-mentioned polymerization gained, and its weight percent is as follows respectively: polyvinyl acetate 2～30%, methyl alcohol 97～65%, sodium hydroxide 1～7%, soft water 0～15%.
2, polyvinyl alcohol synthetic method according to claim 1, it is characterized in that: the polymerization degree of polyvinyl alcohol is 6000～8000, and dispersity is 1.5～2.8.
3, polyvinyl alcohol synthetic method according to claim 2, the dispersity that it is characterized in that polyvinyl alcohol is 1.8～2.5.
4,, it is characterized in that this polyvinyl alcohol is suitable for the PVA fiber of production intensity greater than 20g/d according to claim 1,2 or 3 described polyvinyl alcohol synthetic methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03135392 CN1274726C (en) | 2003-07-09 | 2003-07-09 | Polyvinyl alcohol with high degree of polymerization and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03135392 CN1274726C (en) | 2003-07-09 | 2003-07-09 | Polyvinyl alcohol with high degree of polymerization and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1566165A CN1566165A (en) | 2005-01-19 |
| CN1274726C true CN1274726C (en) | 2006-09-13 |
Family
ID=34470283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03135392 Expired - Lifetime CN1274726C (en) | 2003-07-09 | 2003-07-09 | Polyvinyl alcohol with high degree of polymerization and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1274726C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201405624D0 (en) * | 2014-03-28 | 2014-05-14 | Synthomer Uk Ltd | Method of making a branched polymer, a branched polymer and uses of such a polymer |
| CN110590975A (en) * | 2018-06-12 | 2019-12-20 | 武汉武药科技有限公司 | Medicinal polyvinyl alcohol and preparation method thereof |
| CN111662400A (en) * | 2020-07-06 | 2020-09-15 | 安徽皖维高新材料股份有限公司 | Method for preparing polyvinyl alcohol with high polymerization degree through solution polymerization |
| CN115990440A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | PVAc gel processing system with high polymerization degree |
-
2003
- 2003-07-09 CN CN 03135392 patent/CN1274726C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1566165A (en) | 2005-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109929083B (en) | A kind of multi-block copolymer with narrow molecular weight distribution and preparation method thereof | |
| CN102653580A (en) | Preparation method of Janus-structure composite emulsion particle | |
| Lyoo et al. | Synthesis of high-molecular-weight poly (vinyl alcohol) with high yield by novel one-batch suspension polymerization of vinyl acetate and saponification | |
| CN104961373A (en) | Slump loss resistant type polycarboxylic water reducer and preparation method thereof | |
| CN1274726C (en) | Polyvinyl alcohol with high degree of polymerization and its preparing process | |
| JP2008520821A (en) | Dispersant for producing vinyl chloride resin and method for producing vinyl chloride resin using the same | |
| WO2021196776A1 (en) | Method for preparing branched polyhydroxyethyl methacrylate by inverse emulsion polymerization at room temperature | |
| CN113754844A (en) | A kind of degradable polymer nanomaterial with various morphologies and preparation method thereof | |
| KR102251268B1 (en) | Vinyl chloride polymer and preparation method thereof | |
| CN107236078A (en) | Preparation method of flexible soft monomer colloid photonic crystal emulsion | |
| CN102936305A (en) | Method for preparing branched polymer through suspension polymerization | |
| CN112094371B (en) | Fluorescent thermoplastic polyacrylate elastomer with adjustable mechanical properties and preparation method | |
| CN112812312B (en) | High workability cement dispersion polymer and preparation method thereof | |
| CN110330608A (en) | A kind of preparation method of the photon crystal material of good mechanical performance | |
| CN115947883B (en) | High-quality polyacrylonitrile and controllable synthesis method and application thereof | |
| CN112390906B (en) | Heat-resistant methyl methacrylate polymer and preparation method and application thereof | |
| JP7488183B2 (en) | Polyvinyl alcohol polymer and molded body using same | |
| Zhang et al. | Preparation of polymeric vesicles via redox-initiated RAFT dispersion polymerization | |
| JPS59189111A (en) | Manufacturing method of block copolymer | |
| CN116515029A (en) | Olefin functional polymer and synthetic method and application thereof | |
| CN101386652B (en) | Dispersions containing living radicals | |
| JP2004075822A (en) | Method for producing crosslinked polymer particle | |
| CN116731230A (en) | Preparation method and application of olefin functional polymer | |
| JPH0693016A (en) | Polyvinyl alcohol-based graft copolymer | |
| CN116023604A (en) | Nano-particle of grafted polymer long and short brush and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060913 |