CN114874575B - Low-density small-pore-size polyvinyl formal foam material - Google Patents
Low-density small-pore-size polyvinyl formal foam material Download PDFInfo
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- CN114874575B CN114874575B CN202210724761.6A CN202210724761A CN114874575B CN 114874575 B CN114874575 B CN 114874575B CN 202210724761 A CN202210724761 A CN 202210724761A CN 114874575 B CN114874575 B CN 114874575B
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- 239000006261 foam material Substances 0.000 title claims abstract description 63
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 198
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 195
- 238000006116 polymerization reaction Methods 0.000 claims description 100
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 54
- 239000006260 foam Substances 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 34
- 238000006136 alcoholysis reaction Methods 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000008098 formaldehyde solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- 230000008961 swelling Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000005187 foaming Methods 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 23
- 239000004088 foaming agent Substances 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 181
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- 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
-
- 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
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—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
- C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a low-density small-pore polyvinyl formal foam material and a preparation method thereof. The method does not need to add any pore-forming functional auxiliary agents such as foaming agent, pore-forming agent and the like, and has the advantages of novel method, unique route and good comprehensive performance.
Description
The application is a divisional application, and the original application number is: 202111485125.4, filing date: 2021, 12, 7, title: an open-cell polyvinyl formal foam material and a preparation method thereof.
Technical Field
The invention belongs to the technical field of foam materials, and particularly relates to an open-cell polyvinyl formal foam material and a preparation method thereof.
Technical Field
Polyvinyl alcohol, PVA for short, is a water-soluble and environment-friendly polymer with a large number of hydroxyl groups (-OH) in the side chains. The hydroxyl has high reactivity, and can easily react with various functional reagents to generate the compound with special function. Polyvinyl formal (PVF) foam is a condensation product of polyvinyl alcohol and formaldehyde under acidic conditions, and is a very important class of polymeric materials. PVF foam has strong water absorbability, good hand feeling and elasticity of natural sponge in a wet state, good softness, abundant open-cell structure, excellent wear resistance and weather resistance, high mechanical property, good chemical stability and biocompatibility, and thus has been widely used in many fields.
At present, the main raw materials for producing and preparing PVF foam are polyvinyl alcohol with high polymerization degree, the polymerization degree is more than 1700, such as PVA-1799 (polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 99 percent), PVA-2499 (polyvinyl alcohol with the polymerization degree of 2400 and the alcoholysis degree of 99 percent) and the like. However, when PVF foam is produced using such a high-polymerization-degree polyvinyl alcohol, the foam structure tends to collapse without adding an auxiliary foaming agent, and it is difficult to directly obtain a foam material having an open-cell structure.
In order to solve the technical problems, the prior art and the recent technical report mainly adopt three methods of a foaming agent foaming method, a mechanical foaming method and a pore-foaming agent foaming method to prepare PVF foam. However, in the above-mentioned process, the foaming agent foaming method for preparing PVF foam has the problem of foaming agent residue, which leads to the reduction of the comprehensive properties of the foam; the PVF foam prepared by the mechanical foaming method has the defects of complex process and higher production cost; the porogens used in the foaming process of the porogens to prepare PVF foams generally have some environmental pollution and, in addition, the use of the blowing agents has some cost.
In the previous work, the inventors of the present invention have obtained PVF foams (Li Y, deng J, zhang J.Portus poly (vinyl formal) foam prepared using poly (vinyl alcohol) of low degree of polymerization [ J ]. Polymer International,2018, (67): 1438-1444) having a concentration of PVA-0588 of 14 to 18wt% by enhancing intermolecular interactions by increasing the concentration of polyvinyl alcohol having a low degree of polymerization (PVA-0588, polyvinyl alcohol having a degree of polymerization of 500 and an alcoholysis degree of 88%).
However, in the above publications, it was found and studied that PVF foams could not be formed well at low concentrations or at the same concentrations as prior art high polymerization degree polyvinyl alcohols due to the physical properties of the low polymerization degree polyvinyl alcohols, and could be successfully prepared only at high concentrations. Because no foaming functional reagent is added into the system, the foam material prepared under the condition of high concentration has larger mass density, influences the application range, and the use of the polyvinyl alcohol with high concentration and low polymerization degree greatly increases the cost of the product. In addition, cells in the PVF foam material prepared by using the polyvinyl alcohol with low polymerization degree as a raw material are mostly in a closed cell structure, so that the use of the PVF foam material as the foam material is affected to a certain extent.
Therefore, the light PVF foam with simple process and low cost is explored and developed, and has important practical significance and broad market prospect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an open-cell polyvinyl formal foam material and a preparation method thereof, wherein the preparation method is to obtain the open-cell polyvinyl formal foam material by mixing and dissolving high-polymerization polyvinyl alcohol and low-polymerization polyvinyl alcohol and then reacting with formaldehyde under an acidic condition. The method does not need to add any pore-forming functional auxiliary agents such as foaming agent, pore-forming agent and the like, and has the advantages of novel method, unique route and good comprehensive performance.
In order to achieve the above object, the present invention is realized by adopting the technical scheme comprising the following technical measures.
The open-cell polyvinyl formal foam material comprises the following raw materials in parts by weight:
and a non-foaming, pore-forming functional auxiliary agent;
wherein the total amount of the high-polymerization degree polyvinyl alcohol and the low-polymerization degree polyvinyl alcohol is 8-12 parts, and the total amount of the high-polymerization degree polyvinyl alcohol, the low-polymerization degree polyvinyl alcohol and the deionized water is 100 parts;
the high-polymerization-degree polyvinyl alcohol is polyvinyl alcohol with the polymerization degree of 1700-2600 and the alcoholysis degree of 88-99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 150-500 and the alcoholysis degree of 88-99 percent.
The main invention is that the PVF foam material with an open-cell structure and light weight is obtained by compounding the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree, and the principle is shown in the attached figure 1 of the specification; after the polyvinyl alcohol with low polymerization degree and the polyvinyl alcohol with high polymerization degree are blended, the polyvinyl alcohol with low polymerization degree has short molecular chain and high activity, and can react with formaldehyde in preference to the polyvinyl alcohol with high polymerization degree, and forms a wall pore structure of PVF foam in the mixed solution; after the reaction is carried out for a certain time, the polyvinyl alcohol with high polymerization degree and formaldehyde attach to the wall pore structure formed before to continue the reaction, and with the further improvement of acetalization degree, an open pore structure appears inside. Therefore, PVF foam is prepared by adopting a polyvinyl alcohol compounding method with different polymerization degrees, and PVF foam with uniformly distributed pore structures and light weight can be obtained without adding any pore-forming functional auxiliary agents such as foaming agents, pore-forming agents and the like.
Note that, since no foaming functional auxiliary agent is added in the system, the foaming material does not have expansion characterization in the reaction process, so the inventor theory deduction and comparison experiment prove that the density of the PVF foam material prepared by the method is mainly determined by the concentration of a mixed system (comprising a polyvinyl alcohol solution, a formaldehyde solution and a sulfuric acid solution), and the higher the system concentration is, the higher the material density is; the lower the system concentration is, the lower the material density is, so that the density of the PVF foam material finally prepared can be directly controlled to a certain extent through the concentration regulation and control of each solution in the mixed system, and the foam material density in the prior art is prevented from being greatly influenced by the expansion phenomenon of the foaming agent. In addition, as shown in the figure 2 of the specification, when the concentration of the polyvinyl alcohol mixed solution is high (especially the concentration exceeds 14 percent, calculated by the total amount of the polyvinyl alcohol and the deionized water), the density of the prepared foam material is high, the foam material is converted into rigid foam, and the practicability is greatly reduced; when the concentration of the polyvinyl alcohol mixed solution is low (especially the concentration is not higher than 6%), the concentration of the system is also low, and meanwhile, under the action of gravity, the formed cells are deposited at the bottom of the container, so that the PVF foam material with uniform cell structure distribution and proper density cannot be obtained. Therefore, according to practical experiments, the concentration of the polyvinyl alcohol mixed solution is controlled to be most suitable between 8 and 12 percent based on the experiments.
Secondly, the inventors of the present invention have also found that the pore size of the PVF foam produced is mainly controlled by the formaldehyde content, with the pore size of the foam gradually decreasing as the formaldehyde content increases. Therefore, PVF foam materials with limited pore sizes can be obtained through the technical scheme of the invention by quantitatively adding formaldehyde solution and assisting empirical summarizing rules.
Generally, the aqueous sulfuric acid solution in the raw materials is an acidic solvent conventionally adopted in the art for preparing polyvinyl formal foam materials by using polyvinyl alcohol, and the person skilled in the art can select an aqueous sulfuric acid solution with proper concentration for process preparation by himself through the prior art documents and industrial production conditions so as to meet the acidic conditions required in the preparation process. To better illustrate the invention and to provide a reference choice of raw materials, the concentration of the aqueous sulfuric acid solution is 40%.
Generally, the aqueous formaldehyde solution in the raw materials is the aqueous formaldehyde solution conventionally adopted in the art for preparing polyvinyl formal foam materials by polyvinyl alcohol, and the person skilled in the art can select the aqueous formaldehyde solution with proper concentration for process preparation by the prior art documents and industrial production conditions. To better illustrate the invention and to provide a reference choice of raw materials, the aqueous formaldehyde solution has a concentration of 38%.
In general, the non-foaming and pore-forming functional auxiliary agent in the raw material is an auxiliary agent which is used according to the prior art and reports and does not have foaming and pore-forming functions, and comprises pigment, reinforcing agent and the like according to the application field of the auxiliary agent. Note that the non-foaming, pore-forming functional auxiliary may alternatively be omitted.
It is noted that the invention is mainly characterized by the combination of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree, and the preparation method thereof can be referred to the preparation method of the PVF foam material conventional in the prior art (but the foaming agent and the pore-forming agent are not required to be added), and the proper preparation method is selected according to specific production conditions. In order to better illustrate the present invention, several preparation methods are provided below for reference, but it is noted that this preparation method is not the only preparation method for the open-celled polyformal foam of the present invention.
Firstly, a preparation method of an open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
wherein the total amount of the high-polymerization degree polyvinyl alcohol and the low-polymerization degree polyvinyl alcohol is 8-12 parts, and the total amount of the high-polymerization degree polyvinyl alcohol, the low-polymerization degree polyvinyl alcohol and the deionized water is 100 parts;
the high-polymerization-degree polyvinyl alcohol is polyvinyl alcohol with the polymerization degree of 1700-2600 and the alcoholysis degree of 88-99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 150-500 and the alcoholysis degree of 88-99 percent;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5-2 h, heating to 90-95 ℃ and keeping stirring and dissolving for 2-6 h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 70-90 ℃ for reaction for 3-5 h, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell PVF foam material.
Secondly, a preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(2-1) preparing the following components in parts by weight:
wherein the total amount of the high-polymerization degree polyvinyl alcohol and the low-polymerization degree polyvinyl alcohol is 8-12 parts, and the total amount of the high-polymerization degree polyvinyl alcohol, the low-polymerization degree polyvinyl alcohol and the deionized water is 100 parts;
the high-polymerization-degree polyvinyl alcohol is polyvinyl alcohol with the polymerization degree of 1700-2600 and the alcoholysis degree of 88-99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 150-500 and alcoholysis degree of 88-99%
(2-2) dividing deionized water into two parts according to the weight parts ratio of the high-polymerization-degree polyvinyl alcohol and the low-polymerization-degree polyvinyl alcohol, mixing the high-polymerization-degree polyvinyl alcohol and the low-polymerization-degree polyvinyl alcohol with the corresponding deionized water respectively, standing and swelling for 0.5-2 h after uniform mixing, heating to 90-95 ℃ and keeping stirring and dissolving for 3-5 h, uniformly mixing the dissolved high-polymerization-degree polyvinyl alcohol aqueous solution and the dissolved low-polymerization-degree polyvinyl alcohol aqueous solution, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(2-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (2-2), uniformly mixing, heating to 70-90 ℃ for reaction for 3-5 h, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell PVF foam material.
Generally, the steps of the preparation method are uniformly mixed and stirred by adopting conventional process means, and reference can be made to the existing preparation process of the polyvinyl formal foam material in the field.
Typically, the cooling to room temperature in the steps (1-2) and (2-2) may be either a static cooling or a conventional industrial cooling method such as water cooling.
Typically, the washing and drying in steps (1-3) and (2-3) are carried out by conventional methods, and reference is also made to the prior art techniques for preparing polyvinyl formal foam.
Wherein, in the steps (1-3) and (2-3), the heating is carried out to 70-80 ℃ for 3-5 h, and because the system comprises sulfuric acid aqueous solution, the temperature rising rate during heating needs to be paid attention, and the skilled person can select a proper temperature rising rate according to the selected sulfuric acid aqueous solution concentration and according to the common general knowledge of chemical industry. In order to better illustrate the invention and provide a technical scheme for reference, the heating to 70-90 ℃ is carried out for 3-5 hours under laboratory conditions, and the heating rate is 2-4 ℃/min.
Further researches of the inventor of the invention find that the higher the polymerization degree of the polyvinyl alcohol with low polymerization degree, the larger the required addition amount is due to the consideration of the material forming rate; the smaller the polymerization degree of the polyvinyl alcohol having a low polymerization degree, the smaller the required addition amount. Conversely, the larger the polymerization degree of the polyvinyl alcohol with high polymerization degree is, the smaller the required addition amount is; the smaller the polymerization degree of the high-polymerization-degree polyvinyl alcohol, the larger the required addition amount.
In order to better illustrate the invention and provide a preferred technical solution:
preferably, the open-cell polyvinyl formal foam material comprises the following raw materials in parts by weight:
wherein the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 300 and alcoholysis degree of 88%;
the concentration of the sulfuric acid aqueous solution is 40%, and the concentration of the formaldehyde aqueous solution is 38%.
According to the above preferred embodiment, the open-celled polyvinyl formal foam obtained has a pore size of 120. Mu.m, and a material density of about 0.1g/cm 3 The water absorption is 10 times.
In addition, in order to further control the pore size of the PVF foam material obtained by preparation, a preferable technical scheme is provided through comparison experimental experience summary:
wherein the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 300 and alcoholysis degree of 88%;
the concentration of the sulfuric acid aqueous solution is 40%, and the concentration of the formaldehyde aqueous solution is 38%.
The control test shows that the pore size of the prepared open-cell polyvinyl formal foam is reduced from 120 μm to 16 μm as the addition amount of formaldehyde aqueous solution is increased from 9 parts to 27 parts.
The above preferred technical solution mainly considers that the commercial space of the polyvinyl alcohol with low polymerization degree is smaller, and usually only the polyvinyl alcohol with low polymerization degree with the polymerization degree of 300 can be provided. When the laboratory of the inventor of the invention is used for self-making polyvinyl alcohol with a polymerization degree of 150 and a low polymerization degree, the PVF foam material prepared can theoretically reach higher water absorption rate.
The invention has the following beneficial effects:
1. according to the invention, the PVF foam material with an open-cell structure and light weight is obtained through the compounding use of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree, and any foaming agent and pore-forming agent are not required to be added, so that the negative influence on the foam material caused by the use of the foaming agent and the pore-forming agent is avoided.
2. The invention researches the special process conditions required by the compounding use of the high-polymerization-degree polyvinyl alcohol and the low-polymerization-degree polyvinyl alcohol, determines the proper concentration of the polyvinyl alcohol mixed solution through a comparative test, and provides guidance for the subsequent further production and research.
3. The invention has excellent industrial value, easy implementation and higher product performance.
Drawings
FIG. 1 is a schematic diagram of the reaction principle of the combination of the high polymerization degree polyvinyl alcohol and the low polymerization degree polyvinyl alcohol.
FIG. 2 is a schematic view showing the effect of the concentration of the polyvinyl alcohol mixed solution on foam molding according to the present invention.
FIG. 3 is an electron micrograph of the open-celled polyvinyl formal foam obtained in example 1 of the present invention.
FIG. 4 is a photograph showing the open-celled polyvinyl formal foam obtained in example 1 of the present invention.
FIG. 5 is a photograph showing a polyvinyl formal foam prepared in comparative example 1 of the present invention. It is evident that a closed cell foam structure is present and is converted to a rigid foam.
FIG. 6 is a photograph showing a polyvinyl formal foam prepared in comparative example 2 of the present invention. It is evident that the deposit is at the bottom of the container.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given should not be construed as limiting the scope of the present invention, but rather as merely providing for the benefit of this disclosure.
The following examples and comparative examples used the following types and sources of reagents:
PVA-1799: a polyvinyl alcohol having a polymerization degree of 1799 and an alcoholysis degree of 99%;
PVA-0588: a polyvinyl alcohol having a polymerization degree of 500 and an alcoholysis degree of 88%;
PVA-0388: a polyvinyl alcohol having a degree of polymerization of 300 and an alcoholysis of 88%;
PVA-150: polyvinyl alcohol with a degree of polymerization of 150 and an alcoholysis of 99%;
formaldehyde: configured as a 38% aqueous solution;
sulfuric acid: configured as a 40% aqueous solution.
The performance test method and the instrument are as follows:
1. and (5) topography analysis. The cross-sectional morphology of PVF foam was observed by using a scanning electron microscope type S-3400 of Hitachi, japan, and the acceleration voltage was 15kV. The test sample is quenched under liquid nitrogen, and all the cross sections of the sample are sprayed with a layer of gold to improve the resolution of the photo and reduce static electricity. And the size of the PVF foam cells was counted using Image-Pro Plus software.
2. Density. The density of PVF foam is measured using the geometric method according to International Standard ISO845:2006, and the calculation formula is as follows:
ρ＝m/v
where ρ is the density of the PVF foam and m and v represent the mass and volume, respectively, of the PVF foam sample.
3. Water absorption test. The water absorption of PVF foam was tested using the traditional gravimetric method: briefly, the weight of the dry PVF foam was weighed using an analytical balance, and the PVF foam was then immersed in distilled water at room temperature; at predetermined time intervals, the PVF foam was removed, water on the surface of the PVF foam was carefully wiped off with filter paper, and then the weight of the PVF foam was measured again. The calculation formula of the equilibrium swelling degree is as follows:
wherein S is the swelling degree of the PVF foam, m s Is the weight of PVF foam after swelling; m is m d Is the weight of the dry PVF foam.
Example 1
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 150 and the alcoholysis degree of 99 percent;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5h, heating to 90 ℃, keeping stirring and dissolving for 6h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
The open-cell polyvinyl formal foam prepared in this example has a pore size of 102 μm and a material density of about 0.1g/cm 3 The water absorption is 10 times.
Example 2
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the polyvinyl alcohol with high polymerization degree is PVA-1799;
the polyvinyl alcohol with low polymerization degree is PVA-0388;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5h, heating to 90 ℃, keeping stirring and dissolving for 6h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
The open-cell polyvinyl formal foam prepared in this example has a pore size of 320 μm and a material density of about 0.1g/cm 3 The water absorption was 9 times.
Example 3
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the polyvinyl alcohol with high polymerization degree is PVA-1799;
the polyvinyl alcohol with low polymerization degree is PVA-0388;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5h, heating to 90 ℃, keeping stirring and dissolving for 6h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
The open-cell polyvinyl formal foam prepared in this example has a pore size of 16. Mu.m, and a material density of about 0.1g/cm 3 The water absorption is 3 times.
Example 4
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the polyvinyl alcohol with high polymerization degree is PVA-1799;
the polyvinyl alcohol with low polymerization degree is PVA-150;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5h, heating to 90 ℃, keeping stirring and dissolving for 6h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
The open-cell polyvinyl formal foam prepared in this example has a pore size of 102 μm and a material density of about 0.1g/cm 3 The water absorption was 11 times.
Example 5
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the polyvinyl alcohol with high polymerization degree is PVA-1799;
the polyvinyl alcohol with low polymerization degree is PVA-150;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5h, heating to 90 ℃, keeping stirring and dissolving for 6h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
The open-cell polyvinyl formal foam prepared in this example has a pore size of 120. Mu.m, and a material density of about 0.1g/cm 3 The water absorption is 8 times.
Example 6
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the polyvinyl alcohol with high polymerization degree is PVA-1799;
the polyvinyl alcohol with low polymerization degree is PVA-0588;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5h, heating to 90 ℃, keeping stirring and dissolving for 6h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
The open-cell polyvinyl formal foam prepared in this example has a pore size of 38. Mu.m, and a material density of about 0.1g/cm 3 The water absorption was 7 times.
Example 7
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the polyvinyl alcohol with high polymerization degree is PVA-1799;
the polyvinyl alcohol with low polymerization degree is PVA-0588;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5h, heating to 90 ℃, keeping stirring and dissolving for 6h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
The open-cell polyvinyl formal foam prepared in this example has a pore size of 227. Mu.m, and a material density of about 0.1g/cm 3 The water absorption was 7 times.
Example 8
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 300 and alcoholysis degree of 88%;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 2 hours, heating to 95 ℃, keeping stirring and dissolving for 4 hours, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 90 ℃ for reaction for 5 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
Example 9
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 300 and alcoholysis degree of 88%;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 1h, heating to 95 ℃, keeping stirring and dissolving for 2h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 70 ℃ for reaction for 3 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
Example 10
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(2-1) preparing the following components in parts by weight:
the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 300 and alcoholysis degree of 88%;
(2-2) mixing the high-polymerization-degree polyvinyl alcohol and the low-polymerization-degree polyvinyl alcohol with deionized water according to weight fractions respectively, standing and swelling for 1h after uniform mixing, heating to 90 ℃ and keeping stirring for dissolving for 4h, uniformly mixing the dissolved high-polymerization-degree polyvinyl alcohol aqueous solution and the dissolved low-polymerization-degree polyvinyl alcohol aqueous solution, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(2-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (2-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
Comparative example 1
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 150 and the alcoholysis degree of 99 percent;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5h, heating to 90 ℃, keeping stirring and dissolving for 6h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, and thus obtaining the polyvinyl formal foam material.
The PVF foam material prepared in this comparative example was tested to have a material density of 0.3g/cm 3 The water absorption was 0.5 times and converted to a rigid foam as shown in figure 5.
Comparative example 2
The preparation method of the open-cell polyvinyl formal foam material comprises the following steps:
(1-1) preparing the following components in parts by weight:
the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 150 and the alcoholysis degree of 99 percent;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5h, heating to 90 ℃, keeping stirring and dissolving for 6h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃ for reaction for 4 hours, washing and drying the obtained product after the reaction time is over, thus obtaining the open-cell polyvinyl formal foam material.
The polyvinyl formal material prepared in this comparative example was tested to be deposited on the bottom of the container, losing the inherent properties of the foam material, as shown in fig. 6.
Claims (4)
1. The low-density small-pore polyvinyl formal foam material is characterized by comprising the following raw materials in parts by weight:
7 parts of polyvinyl alcohol with high polymerization degree,
3 parts of polyvinyl alcohol with low polymerization degree,
90 parts of deionized water,
20 parts of sulfuric acid aqueous solution,
27 parts of formaldehyde aqueous solution;
the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 300 and alcoholysis degree of 88%;
the concentration of the sulfuric acid aqueous solution is 40%;
the concentration of the aqueous formaldehyde solution was 38%.
2. The low density, small pore polyvinyl formal foam of claim 1, wherein: the raw materials also comprise non-foaming and pore-forming functional auxiliary agents.
3. The low density, small pore polyvinyl formal foam of claim 2, wherein: the non-foaming pore-forming functional auxiliary agent is selected from any one or more of pigment and reinforcing agent.
4. The low-density small-pore polyvinyl formal foam of claim 1, characterized in that the preparation method comprises the following steps:
(1-1) preparing the following components in parts by weight:
7 parts of polyvinyl alcohol with high polymerization degree,
3 parts of polyvinyl alcohol with low polymerization degree,
90 parts of deionized water,
20 parts of sulfuric acid aqueous solution,
27 parts of formaldehyde aqueous solution;
the high-polymerization-degree polyvinyl alcohol is 1799-degree polyvinyl alcohol with 99% alcoholysis degree;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 300 and alcoholysis degree of 88%;
(1-2) adding high-polymerization-degree polyvinyl alcohol and low-polymerization-degree polyvinyl alcohol into deionized water, uniformly mixing, standing and swelling for 0.5-2 h, heating to 90-95 ℃, keeping stirring and dissolving for 2-6 h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
(1-3) adding formaldehyde aqueous solution and sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 70-90 ℃ for reaction for 3-5 h, washing and drying the obtained product after the reaction time is over, and thus obtaining the open-cell PVF foam material.
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