CN113121937A - Thermoplastic modified polyvinyl alcohol microporous foamed collodion and preparation process thereof - Google Patents
Thermoplastic modified polyvinyl alcohol microporous foamed collodion and preparation process thereof Download PDFInfo
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- CN113121937A CN113121937A CN202010027366.3A CN202010027366A CN113121937A CN 113121937 A CN113121937 A CN 113121937A CN 202010027366 A CN202010027366 A CN 202010027366A CN 113121937 A CN113121937 A CN 113121937A
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- Prior art keywords
- polyvinyl alcohol
- modified polyvinyl
- thermoplastic modified
- collodion
- microcellular foam
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- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- 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
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- 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)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The thermoplastic modified polyvinyl alcohol microporous foamed collodion comprises the following components in percentage by weight: 97.5% -99.5%, cross-linking agent: 0% -1%, foaming agent: 0.5 to 1.5 percent. A preparation process of thermoplastic modified polyvinyl alcohol microcellular foam collodion cotton comprises the following steps: mixing thermoplastic modified polyvinyl alcohol and a crosslinking agent by a mixer, adding the mixture from a hopper, and performing melt extrusion by a double screw at the temperature of 180-210 ℃; the foaming agent is conveyed into an extruder through a metering pump and is fully fused with materials through a screw to form a homogeneous solution, then the pressure is rapidly reduced to enable dissolved gas to rapidly form bubble nuclei, the solution containing bubbles is injected into a forming device for forming and curing, the pressure is 60-100 MPa and the temperature is 25-35 ℃ during forming and curing. The invention overcomes the problem that the polyvinyl alcohol is difficult to be processed by hot molding due to the fusion temperature and the decomposition temperature of the polyvinyl alcohol are close; the one-time processing molding efficiency is high; the pollution of waste water and waste gas is reduced.
Description
Technical Field
The invention relates to the technical field of processing of cleaning product foaming materials, in particular to thermoplastic modified polyvinyl alcohol microcellular foaming collodion cotton and a preparation process thereof.
Background
In the prior art, all collodions for cleaning products are made from water-soluble PVA as a raw material, and because the melting temperature and the decomposition temperature of the PVA are very close to each other, the PVA is dissolved at high temperature after being added with water, and is subjected to acetalation reaction with formaldehyde under the catalysis of acid, and starch or other low-boiling point substances are used as pore-forming agents to prepare a three-dimensional network-shaped cross-linked structure, so that a large amount of acid and formaldehyde steam can be generated in the production process, a large amount of water resources are consumed in the later cleaning process, and the organic pore-forming agents can also cause eutrophication of water and can be cured for tens of hours. In the existing pigment type water-based color paste, a micromolecular surfactant is used as a dispersing agent, wheat starch is used as a pore-forming agent in the forming and curing process of polyvinyl formal collodion, ester substances in the wheat starch also have surface activity and can generate a synergistic effect with the dispersing agent in the color paste, the solubility of pigment particles in water after the collodion is formed is improved, and the collodion is washed and faded. Therefore, the development of a collodion processing technology which has high forming efficiency, reduces the pollution of waste water and waste gas and avoids the washing and fading of the collodion is urgently needed.
Disclosure of Invention
Aiming at the problems brought forward by the background technology, the invention researches and designs a thermoplastic modified polyvinyl alcohol microcellular foam collodion cotton and a preparation process thereof, and the purpose is as follows: the thermoplastic modified polyvinyl alcohol microporous foamed collodion cotton has high forming efficiency, reduces the pollution of waste water and waste gas, and avoids the color fading of the collodion cotton after washing and the preparation process thereof.
The technical solution of the invention is as follows:
a thermoplastic modified polyvinyl alcohol microcellular foam collodion is characterized in that: the weight percentage of each component is as follows:
thermoplastic modified polyvinyl alcohol: 97.5 percent to 99.5 percent;
a crosslinking agent: 0% -1%;
foaming agent: 0.5 to 1.5 percent.
Further, the cross-linking agent is one of ditert-butane peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-ditert-butyl-hexane peroxide, 2, 5-dimethyl-2, 5-ditert-butyl-hexyne peroxide, 1, 3-ditert-butyl-cumene peroxide and isocyanate.
Further, the foaming agent is one of supercritical carbon dioxide and supercritical nitrogen.
Further, the thermoplastic modified polyvinyl alcohol is one of ethylene-vinyl alcohol resin and thermoplastic polyvinyl formal resin.
Further, the ethylene content in the ethylene-vinyl alcohol resin is 20-45%.
A preparation process of thermoplastic modified polyvinyl alcohol microcellular foam collodion cotton is characterized by comprising the following steps: the method comprises the following steps: mixing the thermoplastic modified polyvinyl alcohol and the cross-linking agent by a mixer, adding the mixture from a hopper, and performing melt extrusion by a double screw at the temperature of 180-210 ℃; and conveying the foaming agent into an extruder through a metering pump, fully fusing the foaming agent with the material through a screw to form a homogeneous solution, quickly reducing the pressure to enable the dissolved gas to quickly form a bubble nucleus, injecting the bubble-containing solution into a forming device for forming and curing, wherein the pressure during forming and curing is 60-100 MPa, and the temperature is 25-35 ℃ to obtain the thermoplastic modified polyvinyl alcohol microcellular foamed collodion cotton product.
Preferably, the melt extrusion temperature is 200 ℃.
Preferably, the pressure of the forming and curing is 100MPa, and the temperature is 30 ℃.
The thermoplastic modified polyvinyl alcohol microcellular foam collodion cotton product adopts extrusion cooling when the shape is single.
When the thermoplastic modified polyvinyl alcohol microporous foamed collodion cotton product is a flat plate or a large block, compression molding and later-stage cutting are adopted.
The invention has the beneficial effects that: the invention takes the thermoplastic modified polyvinyl alcohol as the main material, and overcomes the problem that the polyvinyl alcohol is difficult to be processed by thermoplastic processing due to the fusion temperature and the decomposition temperature of the polyvinyl alcohol are close; the one-time processing molding efficiency is high; and a large amount of acid, aldehyde and other additives are not needed, so that the pollution of waste water and waste gas is reduced, and the method can be popularized and used in a large range.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1: 97.5 percent of ethylene-vinyl alcohol resin (the content of ethylene is 35 percent) and 1 percent of dicumyl peroxide as a crosslinking agent are mixed by a mixer and then added by a hopper, and the mixture is melted and extruded by a double screw, and the extrusion temperature is 200 ℃; conveying 1% of supercritical carbon dioxide foaming agent into an extruder through a metering pump, fully fusing the supercritical carbon dioxide foaming agent with materials through a screw to form homogeneous solution, then quickly reducing the pressure to enable the dissolved gas to quickly form countless bubble nuclei, enabling the melt containing a large amount of bubbles to flow into a forming device for forming and curing, wherein the pressure during forming and curing is 100MPa, and the temperature is 30 ℃ to obtain the thermoplastic modified polyvinyl alcohol microcellular foamed collodion cotton product.
Example 2: 97.5 percent of ethylene-vinyl alcohol resin (the content of ethylene is 20 percent) and 1 percent of crosslinking agent ditert-butane peroxide are mixed by a mixer and then added by a hopper, and the mixture is melted and extruded by a double screw, and the extrusion temperature is 200 ℃; conveying 1% of the supercritical nitrogen foaming agent into an extruder through a metering pump, fully fusing the supercritical nitrogen foaming agent with materials through a screw to form a homogeneous solution, then quickly reducing the pressure to enable the dissolved gas to quickly form countless bubble nuclei, enabling the solution containing a large amount of bubbles to flow into a forming device for forming and curing, and obtaining the thermoplastic modified polyvinyl alcohol microcellular foamed collodion cotton product at the pressure of 70MPa and the temperature of 25 ℃ during forming and curing.
Example 3: adding 99 percent of ethylene-vinyl alcohol resin (the content of ethylene is 35 percent) from a hopper, and performing melt extrusion by a double screw, wherein the extrusion temperature is 190 ℃; conveying 1% of supercritical carbon dioxide foaming agent into an extruder through a metering pump, fully fusing the supercritical carbon dioxide foaming agent with materials through a screw to form a homogeneous solution, then quickly reducing the pressure to enable the dissolved gas to quickly form countless bubble nuclei, enabling the solution containing a large amount of bubbles to flow into a forming device for forming and curing, and obtaining the thermoplastic modified polyvinyl alcohol microcellular foamed collodion cotton product at the pressure of 80MPa and the temperature of 30 ℃ during forming and curing.
Example 4: adding 97.5 percent of thermoplastic polyvinyl formal resin from a hopper, and performing melt extrusion by a double screw, wherein the extrusion temperature is 210 ℃; conveying 1% of the supercritical nitrogen foaming agent into an extruder through a metering pump, fully fusing the supercritical nitrogen foaming agent with materials through a screw to form a homogeneous solution, then quickly reducing the pressure to enable the dissolved gas to quickly form countless bubble nuclei, enabling the solution containing a large amount of bubbles to flow into a forming device for forming and curing, and obtaining the thermoplastic modified polyvinyl alcohol microcellular foamed collodion cotton product at the pressure of 90MPa and the temperature of 35 ℃ during forming and curing.
The thermoplastic modified polyvinyl alcohol microcellular foam collodion cotton products prepared in examples 1-4 and collodion cotton products prepared in the prior art (comparative example 1) are subjected to performance tests, and the test results are shown in Table 1:
TABLE 1
The invention takes partially alcoholyzed polyvinyl alcohol aqueous solution as a pigment dispersant, the non-alcoholyzed acetate group of the pigment dispersant is a hydrophobic group which is adsorbed with pigment particles, a long-chain hydrophilic group extends into water, and the steric hindrance of a polyvinyl alcohol polymer chain ensures the continuous dispersion of the pigment particles in a water phase and participates in the subsequent acetalization reaction. Avoids various defects caused by the small molecular surfactant, such as shrinkage and depression caused by insufficient adhesive force between the collodion and the mould, and fading of wheat starch or corn starch when the wheat starch or corn starch is used as a pore-forming agent. The water-based color paste has good compatibility with the conventional starch pore former, and residual water twisted out when collodion made by the common color paste by taking wheat flour as the pore former is pulled out of a mould contains a large amount of pigment and is continuously faded in the subsequent cleaning process; the aqueous color paste has good compatibility with the conventional starch pore-forming agent, the residual water is clear during pattern drawing, and the color can not fade after cleaning.
As is clear from Table 1, the low-cost cereal starch is used as the pore-forming agent and does not fade, so that the raw material cost is saved, the later-stage cleaning times are reduced, consumers can not suffer from the trouble of fading in later-stage use, the surface defect caused by the small-molecular surfactant is avoided, the yield is improved, the water absorption rate and the tensile strength of the low-cost cereal starch are remarkably improved, the production cost is greatly reduced, the production time is greatly shortened, and the low-cost cereal starch pore-forming agent can be popularized and used in a large range.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A thermoplastic modified polyvinyl alcohol microcellular foam collodion is characterized in that: the weight percentage of each component is as follows:
thermoplastic modified polyvinyl alcohol: 97.5 to 99.5 percent
A crosslinking agent: 0 to 1 percent
Foaming agent: 0.5 to 1.5 percent.
2. The thermoplastic modified polyvinyl alcohol microcellular foam collodion as claimed in claim 1, wherein: the cross-linking agent is one of ditert-butane peroxide, dicumyl peroxide, 2,5 dimethyl-2, 5 di-tert-butyl hexane peroxide, 2,5 dimethyl-2, 5 di-tert-butyl hexyne peroxide, 1, 3-di-tert-butyl cumene peroxide and isocyanate.
3. The thermoplastic modified polyvinyl alcohol microcellular foam collodion as claimed in claim 1, wherein: the foaming agent is one of supercritical carbon dioxide and supercritical nitrogen.
4. The thermoplastic modified polyvinyl alcohol microcellular foam collodion as claimed in claim 1, wherein: the thermoplastic modified polyvinyl alcohol is one of ethylene-vinyl alcohol resin and thermoplastic polyvinyl formal resin.
5. The thermoplastic modified polyvinyl alcohol microcellular foam collodion as claimed in claim 4, wherein: the ethylene content in the ethylene-vinyl alcohol resin is 20-45%.
6. The process for preparing the thermoplastic modified polyvinyl alcohol microcellular foam collodion as claimed in claim, wherein: the method comprises the following steps: mixing the thermoplastic modified polyvinyl alcohol and the cross-linking agent by a mixer, adding the mixture from a hopper, and performing melt extrusion by a double screw at the temperature of 180-210 ℃; and conveying the foaming agent into an extruder through a metering pump, fully fusing the foaming agent with the material through a screw to form a homogeneous solution, quickly reducing the pressure to enable the dissolved gas to quickly form a bubble nucleus, injecting the bubble-containing solution into a forming device for forming and curing, wherein the pressure during forming and curing is 60-100 MPa, and the temperature is 25-35 ℃ to obtain the thermoplastic modified polyvinyl alcohol microcellular foamed collodion cotton product.
7. The process for preparing thermoplastic modified polyvinyl alcohol microcellular foam collodion as claimed in claim 6, wherein: the melt extrusion temperature was 200 ℃.
8. The process for preparing thermoplastic modified polyvinyl alcohol microcellular foam collodion as claimed in claim 6, wherein: the pressure of the molding and curing is 100MPa, and the temperature is 30 ℃.
9. The process for preparing thermoplastic modified polyvinyl alcohol microcellular foam collodion as claimed in claim 6, wherein: the thermoplastic modified polyvinyl alcohol microcellular foam collodion cotton product adopts extrusion cooling when the shape is single.
10. The process for preparing thermoplastic modified polyvinyl alcohol microcellular foam collodion as claimed in claim 6, wherein: when the thermoplastic modified polyvinyl alcohol microporous foamed collodion cotton product is a flat plate or a large block, compression molding and later-stage cutting are adopted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010027366.3A CN113121937A (en) | 2020-01-10 | 2020-01-10 | Thermoplastic modified polyvinyl alcohol microporous foamed collodion and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010027366.3A CN113121937A (en) | 2020-01-10 | 2020-01-10 | Thermoplastic modified polyvinyl alcohol microporous foamed collodion and preparation process thereof |
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| CN101003646A (en) * | 2006-12-25 | 2007-07-25 | 刘津平 | Method for producing foamable biomaterial and products of biological foam |
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| CN108543108A (en) * | 2018-05-02 | 2018-09-18 | 山东虎力机械有限公司 | A kind of department of anesthesia often uses sterilizing sponge |
| CN109486071A (en) * | 2018-10-30 | 2019-03-19 | 南京聚隆科技股份有限公司 | A kind of fretting map pad pasting wrapping paper material and preparation method thereof |
| CN110358133A (en) * | 2019-07-17 | 2019-10-22 | 江苏锐康新材料科技有限公司 | A kind of acrylate foamed polymer of substitution for PVA collodion and preparation method thereof |
-
2020
- 2020-01-10 CN CN202010027366.3A patent/CN113121937A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1457342A (en) * | 2001-02-28 | 2003-11-19 | 三井化学株式会社 | Process for production of modified thermoplastic resins and modified thermoplastic resins |
| CN1557872A (en) * | 2004-02-04 | 2004-12-29 | 安徽大维新材有限责任公司 | Highly absorbent polyvinyl alcohol foam and process for preparing same |
| CN1939967A (en) * | 2005-09-30 | 2007-04-04 | 李小鲁 | Hydrophobic degradable biological material, its production and foaming products |
| CN101003646A (en) * | 2006-12-25 | 2007-07-25 | 刘津平 | Method for producing foamable biomaterial and products of biological foam |
| CN101966409A (en) * | 2010-11-05 | 2011-02-09 | 谭明宁 | Novel macromolecular filter material and preparation method thereof |
| CN102020816A (en) * | 2010-11-16 | 2011-04-20 | 谭明宁 | Polyvinyl formal sponge material with uniform abscesses and rapid imbibition and preparation method thereof |
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| CN103554801A (en) * | 2013-08-28 | 2014-02-05 | 谭明宁 | Modified polyvinyl alcohol sponge and preparation method thereof |
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| CN110358133A (en) * | 2019-07-17 | 2019-10-22 | 江苏锐康新材料科技有限公司 | A kind of acrylate foamed polymer of substitution for PVA collodion and preparation method thereof |
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