CN114621493A - Production method of polyvinyl alcohol sponge - Google Patents
Production method of polyvinyl alcohol sponge Download PDFInfo
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- CN114621493A CN114621493A CN202210414975.3A CN202210414975A CN114621493A CN 114621493 A CN114621493 A CN 114621493A CN 202210414975 A CN202210414975 A CN 202210414975A CN 114621493 A CN114621493 A CN 114621493A
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- foaming
- polyvinyl acetal
- polyvinyl
- substance
- acetal resin
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 43
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 238000005187 foaming Methods 0.000 claims abstract description 76
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 64
- 239000011354 acetal resin Substances 0.000 claims abstract description 46
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001241 acetals Chemical class 0.000 claims abstract description 25
- 239000006260 foam Substances 0.000 claims abstract description 25
- 239000000084 colloidal system Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000003292 glue Substances 0.000 claims abstract description 16
- 238000007493 shaping process Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000012766 organic filler Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000004640 Melamine resin Substances 0.000 claims description 3
- 229920000881 Modified starch Polymers 0.000 claims description 3
- 239000004368 Modified starch Substances 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 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
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019426 modified starch Nutrition 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 239000000123 paper Substances 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims 1
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 229920000548 poly(silane) polymer Polymers 0.000 claims 1
- -1 polyol ester Chemical class 0.000 claims 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 9
- 238000005520 cutting process Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000006359 acetalization reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229920001220 nitrocellulos Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a production method of polyvinyl alcohol sponge, which relates to the field of polyvinyl alcohol sponge production, and is characterized in that polyvinyl acetal resin is dissolved in an alcohol water solution to form polyvinyl acetal substance to-be-foamed glue with the mass fraction of 5% -25%; preparing 0.01-3% of foaming substance with high foaming performance by using alcohol water solution, and foaming the foaming substance by using a foaming machine or a foaming machine, or directly stirring and foaming the foaming substance to obtain stable foam slurry; adding the obtained foam slurry into polyvinyl acetal resin adhesive to be foamed, uniformly stirring to obtain foamed colloid, and shaping the foamed colloid by a cooling method to obtain the polyvinyl alcohol sponge. Cleaning and cutting the sponge to obtain a finished product. According to the invention, the polyvinyl acetal resin is directly foamed and then cooled for forming, only physical changes are involved in the foaming production link, chemical changes such as acetal reaction and the like are avoided, a new thought is provided for industrial upgrading of polyvinyl alcohol sponge, and the whole process is clean and environment-friendly without chemical changes.
Description
Technical Field
The invention relates to the field of polyvinyl alcohol sponges, in particular to a production method of a polyvinyl alcohol sponge.
Background
Polyvinyl alcohol sponge means a foam formed from polyvinyl alcohol and an acetal of at least one aldehyde selected from formaldehyde, acetaldehyde, glyoxylic acid, glyoxal, propionaldehyde, acrolein, butyraldehyde, and glutaraldehyde.
The preparation method of the polyvinyl alcohol sponge comprises the following steps: pore-forming agent filling pore-forming method, chemical foaming method, mechanical stirring method and combination of the three methods.
The pore-forming agent is prepared through dissolving PVA, adding pore-forming agent, catalyst, cross-linking agent and other improving or dispersing agent, cross-linking and curing, and removing the pore-forming agent from sponge to obtain porous sponge PVA material. The disadvantages of large environmental protection pressure, low utilization value of starch, large water consumption, and incapability of recycling starch and acid catalyst, thus being not beneficial to saving resources and reducing cost.
The chemical foaming method is that during the production process, substances capable of generating gas (usually carbon dioxide and nitrogen) through chemical reaction, such as carbonates capable of generating reaction with acid, azo substances capable of generating nitrogen through thermal decomposition and the like are added, and then a surfactant is added to play a role in foam homogenizing and stabilizing, so that generated bubbles can be uniformly dispersed in slurry, and the polyvinyl alcohol sponge is obtained after the system is crosslinked and cured. The defects are that the requirements on the process and equipment are high in production, the sponge foam holes of the obtained product are difficult to control uniformly, and a large amount of foam can be generated by residual surfactant in the sponge cleaning link to cause environmental pollution.
The mechanical stirring foaming method is to add surfactant which is easy to generate bubbles through stirring into the system, carry air into the system through high-speed stirring, obtain a certain foaming ratio, and then crosslink and solidify the mixture.
The comprehensive foaming method is characterized in that a chemical foaming method is introduced to generate a certain amount of bubbles in a mechanical stirring foaming process, so that the aim of assisting in foaming is fulfilled.
In the process, the acetalization reaction and the foaming pore-forming are carried out synchronously, namely, the acetalization reaction is carried out synchronously under the action of acid and aldehyde in the foaming forming process. Therefore, the reaction process not only needs to ensure the condition of the acetalization reaction, but also needs to simultaneously take foaming or forming conditions into consideration. Factors influencing the speed of the acetal reaction, such as the addition amount of acid and aldehyde, the addition temperature, the acetal temperature and the like, and have important influence on foaming or molding.
Therefore, the polyvinyl alcohol sponge product production enterprises adopting the process method are influenced by the production conditions such as foaming, acetal and the like, the industries are always dispersed, particularly in weak areas and remote areas of environmental protection supervision, and the large enterprises are few and are basically produced in small factories or workshops. Like PVA collodion cotton head manufacturing enterprise, PVA imitation deerskin towel manufacturing enterprise, PVA face washing puff manufacturing enterprise etc. all need to adopt intermittent type method production, often leads to the following problem to appear: the industry is dispersed, and the large-scale production is difficult; the water consumption is large, the production environmental protection pressure is large, a large amount of wastewater containing acid, aldehyde and organic matters is discharged, and a large amount of acid gas and formaldehyde gas is discharged; the production environment is severe, the production workshop is almost in a water accumulation state throughout the year, and the production in a standard industrial park can not be realized; the energy consumption is high, and a large amount of steam is needed for heating dissolution and heating reaction; the product has poor consistency and is difficult to improve the production scale.
Disclosure of Invention
The invention aims to provide a production method of polyvinyl alcohol sponge, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a production method of polyvinyl alcohol sponge comprises the following steps:
a: preparation of polyvinyl acetal resin glue
Using 35-75% alcohol water solution as solvent, dissolving polyvinyl acetal resin in the alcohol water solution at 25-65 deg.C to prepare 5-25% polyvinyl acetal resin glue;
b: preparation of foamed slurry
Preparing a foaming substance with the mass fraction of 0.01-3% at normal temperature by using an alcohol water solution as a solvent, and foaming the foaming substance by using a bubbler or a foaming machine or directly stirring and foaming the foaming substance to obtain stable foam slurry; the foaming substance is a surfactant with higher foaming activity in an alcohol water solution;
c: foaming of polyvinyl acetal glue
Mixing the foam slurry obtained in the step b and the colloid prepared in the step a together at the temperature of 25-65 ℃ to obtain polyvinyl acetal resin foaming colloid;
the volume ratio of the polyvinyl acetal resin colloid before and after foaming is between 0.1 and 0.9 according to the volume;
d: cooling and shaping of polyvinyl acetal foam
And c, shaping the polyvinyl acetal resin foaming colloid obtained in the step c through a die head, and then cooling and shaping through cold air or cold water.
Preferably, in the step a, an organic or inorganic filler is added to modify the polyvinyl acetal resin, and after foaming molding, polyvinyl alcohol sponge products with different physical and chemical properties are obtained, wherein the filler exists in a polyvinyl acetal resin glue in a dissolved form or a dispersed form, and the adding amount of the filler is 0.1-90% of the mass of the polyvinyl acetal resin glue.
Preferably, the soluble organic filler is an organic substance having a certain solubility in an alcohol aqueous solution.
Preferably, the dispersed organic filler comprises phenolic resin, melamine resin, urea resin, polylactic acid, polyurethane emulsion, pure acrylic emulsion, styrene-acrylic emulsion, EVA emulsion, modified starch, polyacrylic acid, paper fiber, cotton fiber, and various synthetic plastic short fibers or powder.
Preferably, the inorganic filler comprises an abrasive, calcium carbonate powder, attapulgite powder, sepiolite powder, silicon micropowder, putty powder, hydroxyapatite, kaolin, diatomite and bentonite.
Preferably, the foaming method of the polyvinyl acetal glue in the step axis c comprises the following steps: and c, adding the foam slurry obtained in the step b into the colloid prepared in the step a at the temperature of 25-65 ℃, and uniformly stirring.
Preferably, the polyvinyl acetal glue foaming method in the step axis c comprises the following steps: and (c) directly and continuously mixing the foam slurry prepared in the step (b) and the colloid prepared in the step (a) through a mixing head to obtain the polyvinyl acetal resin foamed colloid.
Preferably, the foam-forming substance is a silicone surfactant or a polymeric organic substance that is soluble in an alcohol aqueous solution.
Furthermore, the foam-forming substance is a siloxane substance, a polyether siloxane substance or a siloxane copolymerized polyol substance.
Preferably, the soluble organic matters in the alcohol-water solution are cellulose, chitosan, polyvinyl acetal, polyvinyl butyral, modified carbomer, polyester, sodium alginate, polyacrylamide, sodium polyacrylate, gelatin and protein.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the polyvinyl acetal resin is directly foamed and then cooled for forming, only physical changes are involved in the foaming production link, chemical changes such as acetal reaction and the like are avoided, the whole process is a physical change process, and toxic and harmful chemical substances such as acid, aldehyde and the like are not required to be used. The whole sponge forming step does not involve chemical changes, and a long acetal reaction waiting process is not needed. Provides a new idea for the industrial upgrading of the polyvinyl alcohol sponge.
2. The technology successfully carries out the production of the polyvinyl acetal and the foaming of the polyvinyl acetal resin for segmentation, is favorable for the large-scale supply of the polyvinyl acetal resin, is favorable for the industrialized cultivation of the polyvinyl alcohol sponge, and is favorable for the large-scale production of the polyvinyl alcohol sponge products.
3. The foaming material used is obviously different from the surfactant used in the traditional chemical foaming or gas foaming by adopting gas foaming molding, and a large amount of foam can not be generated in the cleaning link without being cleaned by a large amount of water.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment provides a production method of polyvinyl alcohol sponge, which comprises the following steps:
preparation of polyvinyl acetal resin adhesive
Using 35-75% alcohol water solution as solvent, dissolving polyvinyl acetal resin in the alcohol water solution at 25-65 deg.C to prepare 5-25% polyvinyl acetal resin glue. The polyvinyl acetal resin refers to polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with at least one aldehyde selected from formaldehyde, acetaldehyde, glyoxylic acid, glyoxal, propionaldehyde, acrolein, butyraldehyde and glutaraldehyde under the catalysis of acid. According to the requirements for producing porous sponge products with different properties, the acetalization degree selection interval of the polyvinyl acetal resin is 20-75%, and the average polymerization degree of the polyvinyl alcohol is selected from 500-3000.
In the process of preparing the polyvinyl acetal resin adhesive, organic or inorganic filler can be added to modify the polyvinyl acetal resin so as to obtain polyvinyl alcohol sponge products with different physical properties after foaming and forming. The filler can exist in a dissolved form or a dispersed form in the polyvinyl acetal resin glue, and the preferable soluble form comprises organic fillers such as cellulose, chitosan, sodium alginate, polyacrylamide, sodium polyacrylate, gelatin, protein, or other soluble organic matters in alcohol water solution; preferred dispersed organic fillers include phenol-formaldehyde resin, melamine resin, urea-formaldehyde resin, polylactic acid, polyurethane emulsion, acrylic emulsion, styrene-acrylic emulsion, EVA emulsion, modified starch, polyacrylic acid, paper fiber, cotton fiber, and various synthetic plastic short fibers or powders. Preferred inorganic fillers include abrasives, calcium carbonate powder, attapulgite powder, sepiolite powder, silica micropowder, putty powder, hydroxyapatite, kaolin, diatomaceous earth, bentonite, and the like. The adding amount of the filler is 0.1-90% of the mass of the polyvinyl acetal resin adhesive.
Preparation of foamed slurry
Using alcohol water solution as solvent, preparing foaming substance with mass fraction of 0.01-3% at normal temperature, and foaming with a bubbler or a foaming machine, or directly stirring for foaming to obtain stable foam slurry. The foam-forming substance may be a surfactant having a high foaming activity in an aqueous alcohol solution, preferably a silicone-based surfactant, particularly a polyether silicone-based substance; the organic polymer may be dissolved in an alcohol aqueous solution, and is preferably a polyether siloxane-based substance or the like.
Foaming of polyvinyl acetal glue
And c, adding the foam slurry obtained in the step b into the colloid prepared in the step a at the temperature of 25-65 ℃, and uniformly stirring, or directly and dynamically and continuously mixing the foam slurry prepared in the step b and the colloid prepared in the step a through a mixing stirring head to obtain the polyvinyl acetal resin foamed colloid. The volume ratio of the polyvinyl acetal resin colloid before and after foaming is between 0.1 and 0.9 by volume.
Cooling and shaping of polyvinyl acetal foam
And c, utilizing the characteristic that the polyvinyl acetal resin is soluble in hot alcohol water solution and is easy to gel and solidify when meeting water or after cooling, carrying out shape molding on the polyvinyl acetal resin foaming colloid obtained in the step c through a die head, cooling and shaping through cold air or cold water to obtain sponge, and cleaning and cutting the sponge to obtain a finished product. The technology of the invention can be used for continuously producing products with various shapes.
And c, producing the sponge with fixed shapes such as blocks, spheres, columns and the like, wherein the polyvinyl acetal resin foaming colloid obtained in the step c is injected into a mould with a fixed shape, and is cooled and shaped at the temperature of between 18 ℃ below zero and 30 ℃ to obtain the sponge.
The production of layered and rolled sponge can use the flow-casting strickling method to spread the foamed colloid on the water surface at 5-30 deg.C, and can implement the processes of forming, drawing, cleaning and rolling, etc. The material such as sponge composite mesh cloth, gauze and the like can be coated with the foaming colloid on the composite material by using a coating method, and then the finished product is obtained by processes such as cooling, sizing, cleaning, embossing and the like.
Compared with the traditional production technology, the sponge production forming technical method has the technical advantages of obvious environmental protection, high efficiency, simplicity, convenience and the like. The whole production process is a physical change process, and toxic and harmful chemical substances such as acid, aldehyde and the like are not needed. No chemical change is involved, and no long acetal reaction waiting process is needed. The foaming material used is obviously different from the surfactant used in the traditional chemical foaming or gas foaming by adopting gas foaming molding, and a large amount of foam can not be generated in the cleaning link without being cleaned by a large amount of water.
Compared with the traditional technology that the sponge body with a certain acetalization degree is obtained by heating and preserving heat for a plurality of hours, the traditional mode of batch production is adopted, the cycle is long and the efficiency is low, the sponge is more energy-saving, the forming speed is high, the cycle is short, and the sponge is convenient and quick. Whereas the sponge formation of the conventional art takes several hours.
In the traditional technology, the batch method is adopted to produce the products one by one and one by one, particularly collodion cotton heads, deerskin-imitating towels and other products, so that the consistency among the batches of the products is poor, a large amount of leftover materials are cut off for each batch of the products, and the waste is serious. The sponge forming process can be used for continuous production line operation, and has the advantages of less leftover materials, high yield and low comprehensive cost. The method can be widely applied to the production of various polyvinyl acetal foams, is particularly suitable for the production of sponge products such as cleaning polyvinyl formal sponges, such as collodion cotton heads, imitation deerskin towels, absorbent cotton, cosmetic cotton, absorbent rollers and the like, and is particularly suitable for the production of various medical polyvinyl formal sponges with higher requirements on the cleaning degree.
The foaming and shaping purposes are achieved through the process of physical change, the whole process has no chemical change, and the foaming and shaping process is clean and environment-friendly. The polyvinyl acetal resin which is an upstream raw material in the market has the existing industrial production and large-scale supply chain, but the bottleneck of large-scale production of the polyvinyl alcohol sponge products lies in the foaming problem of the polyvinyl acetal resin. The polyvinyl acetal resin is directly foamed and then cooled for molding, only physical changes are involved in the foaming production link, chemical changes such as acetal reaction and the like are avoided, and a new thought is provided for the industrial upgrading of the polyvinyl alcohol sponge. The technology successfully produces the polyvinyl acetal and carries out segmentation on the polyvinyl acetal resin foaming, thereby being beneficial to the large-scale supply of the polyvinyl acetal resin, the industrialized cultivation of the polyvinyl alcohol sponge and the large-scale production of the polyvinyl alcohol sponge products.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The production method of the polyvinyl alcohol sponge is characterized by comprising the following steps:
a: preparation of polyvinyl acetal resin glue
Using 35-75% alcohol water solution as solvent, dissolving polyvinyl acetal resin in the alcohol water solution at 25-65 deg.C to prepare 5-25% polyvinyl acetal resin glue;
b: preparation of foam slurries
Preparing a foaming substance with the mass fraction of 0.01-3% at normal temperature by using an alcohol water solution as a solvent, and foaming the foaming substance by using a bubbler or a foaming machine or directly stirring and foaming the foaming substance to obtain stable foam slurry; the foam forming substance is a surfactant with high foaming activity in an alcohol water solution;
c: foaming of polyvinyl acetal glue
Mixing the foam slurry obtained in the step b and the colloid prepared in the step a together at the temperature of 25-65 ℃ to obtain polyvinyl acetal resin foaming colloid;
the volume ratio of the polyvinyl acetal resin colloid before and after foaming is between 0.1 and 0.9 according to the volume;
d: cooling and shaping of polyvinyl acetal foam
And c, shaping the polyvinyl acetal resin foaming colloid obtained in the step c through a die head, and then cooling and shaping through cold air or cold water.
2. The method for producing a polyvinyl alcohol sponge according to claim 1, wherein: and (b) adding an organic or inorganic filler in the step (a) to modify the polyvinyl acetal resin, and obtaining polyvinyl alcohol sponge products with different physical properties after foaming and forming, wherein the filler exists in a polyvinyl acetal resin adhesive in a dissolved form or a dispersed form, and the addition amount of the filler is 0.1-90% of the mass of the polyvinyl acetal resin adhesive.
3. The method for producing a polyvinyl alcohol sponge according to claim 2, wherein: the soluble organic filler is organic matter soluble in alcohol water solution, and comprises cellulose, sodium carboxymethyl cellulose, chitosan, polyester, sodium alginate, polyacrylamide, sodium polyacrylate, gelatin, protein, etc.
4. The method for producing a polyvinyl alcohol sponge according to claim 2, wherein: the dispersed organic filler comprises phenolic resin, melamine resin, urea-formaldehyde resin, polylactic acid, polyurethane emulsion, pure acrylic emulsion, styrene-acrylic emulsion, EVA emulsion, modified starch, polyacrylic acid, paper fiber, cotton fiber and various synthetic plastic short fibers or powder.
5. The method for producing polyvinyl alcohol sponge according to claim 2, wherein: the inorganic filler comprises abrasive, calcium carbonate powder, attapulgite powder, sepiolite powder, silicon micropowder, putty powder, hydroxyapatite, kaolin, diatomite and bentonite.
6. The method for producing polyvinyl alcohol sponge according to claim 1, wherein the polyvinyl acetal glue in step c is foamed by the following method: and c, adding the foam slurry obtained in the step b into the colloid prepared in the step a at the temperature of 25-65 ℃, and uniformly stirring.
7. The method for producing polyvinyl alcohol sponge according to claim 1, wherein the polyvinyl acetal glue in step c is foamed by the following method: and (c) directly and continuously mixing the foam slurry prepared in the step (b) and the colloid prepared in the step (a) through a mixing head to obtain the polyvinyl acetal resin foamed colloid.
8. The method for producing a polyvinyl alcohol sponge according to claim 1, wherein: the foam-forming substance is siloxane surfactant or macromolecular organic matter which can be dissolved in alcohol water solution.
9. The method for producing a polyvinyl alcohol sponge according to claim 8, wherein: the foaming substance is at least one of polysilane substance, polyether siloxane substance and siloxane copolymerized polyol ester substance.
10. A method for producing a polyvinyl alcohol sponge according to claim 3 or claim 8, wherein: the macromolecular organic substance which can be dissolved in the alcohol aqueous solution is cellulose, polyvinyl acetal, polyvinyl butyral and polyester.
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