CN115028949A - Light polyvinyl formal foam material with high water absorption rate - Google Patents
Light polyvinyl formal foam material with high water absorption rate Download PDFInfo
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- CN115028949A CN115028949A CN202210726241.9A CN202210726241A CN115028949A CN 115028949 A CN115028949 A CN 115028949A CN 202210726241 A CN202210726241 A CN 202210726241A CN 115028949 A CN115028949 A CN 115028949A
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- 239000006261 foam material Substances 0.000 title claims abstract description 71
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 200
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 197
- 238000006116 polymerization reaction Methods 0.000 claims description 160
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- 239000006260 foam Substances 0.000 claims description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 34
- 238000006136 alcoholysis reaction Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 239000008098 formaldehyde solution Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 230000008961 swelling Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005187 foaming Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 34
- 238000000034 method Methods 0.000 abstract description 20
- 239000004088 foaming agent Substances 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 186
- 239000000047 product Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003361 porogen Substances 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
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000635 electron micrograph 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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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
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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
- 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
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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
- 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
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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
- 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
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- 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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Abstract
The invention provides a light polyvinyl formal foam material with high water absorption rate and a preparation method thereof. The method does not need any pore-forming functional auxiliary agents such as foaming agents, pore-forming agents 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 numbers are: 202111485125.4, filing date: 12 and 7 days 2021, the invention name: 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 chain. The hydroxyl has higher reactivity and can easily react with a plurality of functional reagents to generate a compound with special functional action. Polyvinyl formal (PVF) foams are condensation products of polyvinyl alcohol and formaldehyde under acidic conditions, and are a very important class of polymeric materials. The PVF foam has strong water absorption, has the hand feeling and elasticity of natural sponge in a wet state, has good flexibility, rich open-cell structure, excellent wear resistance and weather resistance, high mechanical property and good chemical stability and biocompatibility, and is widely applied to many fields.
At present, the main raw material for preparing PVF foam is polyvinyl alcohol with high polymerization degree, and the polymerization degree is more than 1700, such as PVA-1799 (polyvinyl alcohol with polymerization degree of 1700 and alcoholysis degree of 99%), PVA-2499 (polyvinyl alcohol with polymerization degree of 2400 and alcoholysis degree of 99%), and the like. However, when PVF foams are produced using such polyvinyl alcohols having a high degree of polymerization, the foam structure tends to collapse without adding an auxiliary blowing agent, and it is difficult to directly obtain a foam having an open-cell structure.
In order to solve the technical problems, the conventional process and the recent technical reports mainly adopt three methods, namely a foaming agent foaming method, a mechanical foaming method, a pore-foaming agent foaming method and the like to prepare the PVF foam. However, in the above-mentioned process, the preparation of PVF foam by foaming agent foaming method has the problem of foaming agent residue, which will result in the reduction of the overall performance of the foam; the mechanical foaming method for preparing PVF foam has the defects of complex process and higher production cost; porogens used in the preparation of PVF foam by the porogens foaming process generally have a certain pollution to the environment, and in addition, the use of the foaming agent also has a certain cost.
In previous research work, the inventor of the present invention obtains PVF foam (Li Y, Deng J, Zhang J. porous poly (vinyl alcohol) with better water absorption of low density used poly (vinyl alcohol) of polymerization [ J ] 1438. International,2018, (67): 1448) in the range of PVA-0588 concentration 14 wt% -18 wt% by increasing the concentration of polyvinyl alcohol with low polymerization degree (PVA-0588, polyvinyl alcohol with polymerization degree of 500, alcoholysis degree of 88%) to enhance intermolecular interaction.
However, in the above-mentioned publications, it was found and studied that a PVF foam could not be formed well at a low concentration or at the same concentration as that of the polyvinyl alcohol having a high degree of polymerization of the prior art due to the physical properties of the polyvinyl alcohol having a low degree of polymerization, and could be successfully prepared only at a high concentration. Because no functional reagent with foaming function is added in the system, the foam material prepared under the condition of high concentration has larger mass density, the application range is influenced, and the application of the polyvinyl alcohol with low degree of polymerization at high concentration greatly increases the cost of the product. In addition, the cells of the PVF foam prepared by using the polyvinyl alcohol with low polymerization degree as the raw material are mostly of closed cell structures, and the use of the PVF foam as the foam is influenced to a certain extent.
Therefore, exploring and developing a light PVF foam with simple process and low cost has important practical significance and broad market prospect.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides an open-cell polyvinyl formal foam material and a preparation method thereof. The method does not need any pore-forming functional auxiliary agents such as foaming agents, pore-forming agents and the like, and has the advantages of novelty, unique route and good comprehensive performance.
In order to achieve the purpose, the invention adopts the technical scheme formed by 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 aid;
wherein the total amount of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree is 8-12 parts, and the total amount of the polyvinyl alcohol with high polymerization degree, the polyvinyl alcohol with low polymerization degree and the deionized water is 100 parts;
the polyvinyl alcohol with high polymerization degree is polyvinyl alcohol with the polymerization degree of 1700-2600 and the alcoholysis degree of 88-99%;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 150-500 and alcoholysis degree of 88% -99%.
The invention has the main invention points 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 chains and high activity, and can react with formaldehyde in preference to the polyvinyl alcohol with high polymerization degree, and a wall pore structure of PVF foam is formed in a mixed solution; after the reaction is carried out for a certain time, the polyvinyl alcohol with high polymerization degree and the formaldehyde attach to the wall pore structure formed before and continue to react, and an open pore structure appears inside along with further improvement of the acetalization degree. Therefore, the PVF foam is prepared by adopting a method of compounding polyvinyl alcohol with different polymerization degrees, and the PVF foam with uniformly distributed pore structures and light weight can be obtained without adding any pore-forming functional auxiliary agents such as a foaming agent, a pore-foaming agent and the like.
It is noted that, because no foaming functional auxiliary agent is added in the system, the foam material does not have the characteristic of expansion in the reaction process, so that the theoretical derivation of the inventor of the present invention and a control experiment prove that the density of the prepared PVF foam material 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, and further the density of the finally prepared PVF foam material can be directly controlled to a certain extent by regulating and controlling the concentration of each solution in the mixed system, so that the foam material density in the prior art is prevented from being greatly influenced by the expansion phenomenon of the foaming agent. In addition, the influence of the concentration of the polyvinyl alcohol mixed solution composed of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree on foam molding is shown in the attached figure 2 in the specification, and 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, and the prepared foam material is converted into rigid foam, so that 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 simultaneously, the formed cells are deposited at the bottom of the container under the action of gravity, so that the PVF foam material with uniform cell structure distribution and proper density cannot be obtained. Therefore, according to practical experiments, based on the experiments, the concentration of the polyvinyl alcohol mixed solution is optimally controlled to be 8-12%.
Secondly, the inventors of the present invention have also found that the pore size of the prepared PVF foam is mainly controlled by the content of formaldehyde, and the pore size of the foam gradually decreases as the content of formaldehyde increases. Therefore, the PVF foam material with limited pore size can be obtained by the technical scheme of the invention through quantitative addition of the formaldehyde solution and auxiliary empirical summary rule.
Generally, the aqueous solution of sulfuric acid in the raw material is an acidic solvent conventionally used in the preparation of polyvinyl formal foam materials by polyvinyl alcohol in the art, and a person skilled in the art can select an aqueous solution of sulfuric acid with a proper concentration for the preparation process by the prior art literature and industrial production conditions to meet the acidic conditions required by the preparation process. To better illustrate the invention and to provide a selection of raw materials for reference, the concentration of the aqueous sulfuric acid solution was 40%.
Generally, the aqueous formaldehyde solution in the raw material is an aqueous formaldehyde solution which is conventionally used in the preparation of polyvinyl formal foam materials by polyvinyl alcohol in the field, and a person skilled in the art can select an aqueous formaldehyde solution with a proper concentration for the preparation process by the prior art documents and industrial production conditions. To better illustrate the invention and to provide a selection of raw materials for reference, the concentration of the aqueous formaldehyde solution was 38%.
Generally, the non-foaming pore-forming functional auxiliary agents in the raw materials are auxiliary agents without foaming and pore-forming functions, including pigments, reinforcing agents and the like, used in the preparation process of the foam materials based on the prior art and reports according to the application field of the foam materials. It is noted that the non-foaming, pore-forming functional aid may alternatively be absent.
It is noted that the invention mainly lies in the compounding use of polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree, and the preparation method thereof can be selected by persons skilled in the art according to specific production conditions by referring to the conventional preparation method of PVF foam material in the prior art (but paying attention to no need of adding foaming agent and pore-forming agent). For a better illustration of the invention, several reference preparations will be provided below, but it is to be noted that this preparation is not the only preparation of the open-celled polyvinyl formal foams of the present invention.
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:
wherein the total amount of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree is 8-12 parts, and the total amount of the polyvinyl alcohol with high polymerization degree, the polyvinyl alcohol with low polymerization degree and the deionized water is 100 parts;
the polyvinyl alcohol with high polymerization degree is polyvinyl alcohol with the polymerization degree of 1700-2600 and the alcoholysis degree of 88-99%;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 150-500 and alcoholysis degree of 88% -99%;
(1-2) adding polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree into deionized water, uniformly mixing, standing for swelling for 0.5-2 h, heating to 90-95 ℃, keeping stirring for dissolving for 2-6 h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
and (1-3) adding a formaldehyde solution and a sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 70-90 ℃, reacting for 3-5 hours, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell PVF foam material.
Secondly, 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:
wherein the total amount of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree is 8-12 parts, and the total amount of the polyvinyl alcohol with high polymerization degree, the polyvinyl alcohol with low polymerization degree and the deionized water is 100 parts;
the polyvinyl alcohol with high polymerization degree is polyvinyl alcohol with the polymerization degree of 1700-2600 and the alcoholysis degree of 88% -99%;
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 part ratio of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree, respectively mixing the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree with corresponding deionized water, standing and swelling for 0.5-2 h after uniform mixing, heating to 90-95 ℃, keeping stirring and dissolving for 3-5 h, uniformly mixing the dissolved polyvinyl alcohol aqueous solution with the polyvinyl alcohol aqueous solution with low polymerization degree, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
and (2-3) adding a formaldehyde solution and a sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (2-2), uniformly mixing, heating to 70-90 ℃, reacting for 3-5 hours, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell PVF foam material.
In general, the steps of the preparation method are uniformly mixed and stirred by adopting conventional process means, and the existing preparation process of the polyvinyl formal foam material in the field can also be referred.
In general, the cooling in steps (1-2) and (2-2) to room temperature may be carried out by standing or by a conventional industrial cooling method such as water cooling.
Generally, the washing and drying in steps (1-3) and (2-3) are carried out by conventional methods, and the existing preparation process of polyvinyl formal foam in the field can be referred to.
Wherein, the heating in the steps (1-3) and (2-3) to 70-80 ℃ for reaction for 3-5 h, and the system comprises the sulfuric acid aqueous solution, so the temperature rise rate during heating needs to be noticed, and a person skilled in the art can select a proper temperature rise rate according to the concentration of the selected sulfuric acid aqueous solution and the chemical general knowledge. In order to better illustrate the invention and provide a reference technical scheme, under the condition of a laboratory, the reaction is carried out for 3-5 hours when the temperature is increased to 70-90 ℃, and the heating rate is 2-4 ℃/min.
Through further research by the inventor of the invention, the proportion of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree is adjusted, so that the higher the polymerization degree of the polyvinyl alcohol with low polymerization degree is, the larger the required addition amount is due to the consideration of the material forming rate; the smaller the degree of polymerization of the polyvinyl alcohol having a low degree of polymerization, the smaller the amount to be added. On the contrary, the larger the polymerization degree of the polyvinyl alcohol with high polymerization degree is, the smaller the required addition amount is; the smaller the degree of polymerization of the polyvinyl alcohol having a high degree of polymerization, the larger the amount to be added.
In order to better illustrate the invention and to provide a preferred solution:
preferably, the open-cell polyvinyl formal foam material comprises the following raw materials in parts by weight:
wherein, the polyvinyl alcohol with high polymerization degree is the polyvinyl alcohol with polymerization degree of 1799 and alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 300 and the 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 preferred embodiment, the open-cell polyvinyl formal foam material prepared has a pore size of 120 μm and a material density of about 0.1g/cm 3 The water absorption was 10 times.
In addition, in order to further control the pore size of the prepared PVF foam material, a preferable technical scheme is provided through the summary of comparative experiment experience:
wherein, the polyvinyl alcohol with high polymerization degree is polyvinyl alcohol with the polymerization degree of 1799 and the alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 300 and the alcoholysis degree of 88 percent;
the concentration of the sulfuric acid aqueous solution is 40%, and the concentration of the formaldehyde aqueous solution is 38%.
Through comparison tests, the pore diameter of the prepared open-cell polyvinyl formal foam material is reduced from 120 μm to 16 μm when the addition amount of the formaldehyde aqueous solution is increased from 9 parts to 27 parts.
The preferred technical proposal mainly considers that the low-polymerization polyvinyl alcohol has small commercial space and can only provide the low-polymerization polyvinyl alcohol with the polymerization degree of 300. When the polyvinyl alcohol with low polymerization degree of 150 is prepared by the inventor in a laboratory, the prepared PVF foam material can theoretically achieve higher water absorption rate.
The invention has the following beneficial effects:
1. according to the invention, through the compound use of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree, the light PVF foam material with an open-cell structure is obtained, and any foaming agent and pore-foaming 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-foaming agent is avoided.
2. The invention researches the unique process conditions required by the compounding of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree, determines the proper concentration of the polyvinyl alcohol mixed solution and the addition proportion of the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree through a comparison 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 high-polymerization degree polyvinyl alcohol and low-polymerization degree polyvinyl alcohol.
FIG. 2 is a schematic diagram showing the effect of the concentration of the polyvinyl alcohol mixed solution of the present invention on foam formation.
FIG. 3 is an electron micrograph of an open-celled polyvinyl formal foam prepared according to example 1 of the present invention.
FIG. 4 is a photograph of an open-celled polyvinyl formal foam material obtained in example 1 of the present invention.
FIG. 5 is a photograph of a polyvinyl formal foam material prepared by comparative example 1 according to the present invention. It is clearly seen as a closed cell foam structure and is transformed into a rigid foam.
FIG. 6 is a photograph of a polyvinyl formal foam material prepared in comparative example 2 according to the present invention. It is clearly visible that deposits are on 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 are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
The following examples and comparative examples employ the following reagent types and sources:
PVA-1799: polyvinyl alcohol with polymerization degree of 1799 and alcoholysis degree of 99%;
PVA-0588: polyvinyl alcohol with the polymerization degree of 500 and the alcoholysis degree of 88 percent;
PVA-0388: polyvinyl alcohol with the polymerization degree of 300 and the alcoholysis degree of 88 percent;
PVA-150: polyvinyl alcohol with the polymerization degree of 150 and the alcoholysis degree of 99 percent;
formaldehyde: preparing a 38% aqueous solution;
sulfuric acid: the mixture was prepared as a 40% aqueous solution.
The performance test method and the apparatus are as follows:
1. and (5) analyzing the appearance. The cross-sectional morphology of the PVF foam was observed using a scanning electron microscope, model S-3400, from Hitachi, Japan, at an acceleration voltage of 15 kV. The test samples were quenched in liquid nitrogen and all sample sections were coated with gold to improve the resolution of the photographs and reduce static. And the size of the PVF foam cells was counted using Image-Pro Plus software.
2. Density. The density of the PVF foam is measured according to the international standard ISO845:2006 by using a geometric method, 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. And (5) testing water absorption. The water absorption of the PVF foam was tested using conventional gravimetric methods: briefly, dry PVF foam was weighed using an analytical balance and then immersed in distilled water at room temperature; at predetermined time intervals, the PVF foam was removed, the surface of the PVF foam was carefully wiped off with filter paper to remove water, and then the weight of the PVF foam was measured again. The equilibrium swelling degree is calculated as follows:
wherein S is the degree of swelling of the PVF foam, m s Is the weight of the PVF foam after swelling; m is 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 polyvinyl alcohol with high polymerization degree is the polyvinyl alcohol with polymerization degree of 1799 and alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 150 and alcoholysis degree of 99 percent;
(1-2) adding polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell polyvinyl formal foam material.
As a result of testing, the open-cell polyvinyl formal foam material prepared in this example had a cell size of 102 μm and a material density of about 0.1g/cm 3 The water absorption was 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 polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell polyvinyl formal foam material.
As a result of testing, the open-cell polyvinyl formal foam material prepared in this example had 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 polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell polyvinyl formal foam material.
As a result of testing, the open-cell polyvinyl formal foam prepared in this example had a pore diameter of 16 μm and a material density of about 0.1g/cm 3 The water absorption was 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 polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell polyvinyl formal foam material.
As a result of testing, the open-cell polyvinyl formal foam material prepared in this example had a cell 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 polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell polyvinyl formal foam material.
As a result of testing, the open-cell polyvinyl formal foam material prepared in this example had a cell size of 120 μm and a material density of about 0.1g/cm 3 The water absorption was 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 polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 80 ℃, reacting for 4 hours, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell polyvinyl formal foam material.
As a result of testing, the open-cell polyvinyl formal foam prepared in this example had a pore size of 38 μm 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 polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell polyvinyl formal foam material.
As a result of testing, the open-cell polyvinyl formal foam material prepared in this example had a cell size of 227 μm 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 polyvinyl alcohol with high polymerization degree is the polyvinyl alcohol with polymerization degree of 1799 and alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 300 and the alcoholysis degree of 88 percent;
(1-2) adding polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain 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 polyvinyl alcohol with high polymerization degree is polyvinyl alcohol with the polymerization degree of 1799 and the alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 300 and the alcoholysis degree of 88 percent;
(1-2) adding polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain 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 polyvinyl alcohol with high polymerization degree is the polyvinyl alcohol with polymerization degree of 1799 and alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with the polymerization degree of 300 and the alcoholysis degree of 88 percent;
(2-2) respectively mixing the polyvinyl alcohol with high polymerization degree and the polyvinyl alcohol with low polymerization degree with deionized water according to weight fractions, standing and swelling for 1h after uniform mixing, heating to 90 ℃, keeping stirring and dissolving for 4h, uniformly mixing the dissolved polyvinyl alcohol aqueous solution with the polyvinyl alcohol aqueous solution with low polymerization degree, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
and (2-3) adding a formaldehyde solution and a sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (2-2), uniformly mixing, heating to 80 ℃, reacting for 4 hours, and after the reaction time is over, washing and drying the obtained product to obtain 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 polyvinyl alcohol with high polymerization degree is the polyvinyl alcohol with polymerization degree of 1799 and alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 150 and alcoholysis degree of 99 percent;
(1-2) adding polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain 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 the foam was converted into a rigid foam, as shown in FIG. 5.
Comparative example 2
The comparative example is a preparation method of open-cell polyvinyl formal foam material, comprising the following steps:
(1-1) preparing the following components in parts by weight:
the polyvinyl alcohol with high polymerization degree is the polyvinyl alcohol with polymerization degree of 1799 and alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 150 and alcoholysis degree of 99 percent;
(1-2) adding polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree 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;
and (1-3) adding a formaldehyde solution and a 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, and after the reaction time is over, washing and drying the obtained product to obtain 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 and lost the inherent properties of the foam, as shown in figure 6.
Claims (6)
1. A light polyvinyl formal foam material with high water absorption rate is characterized in that the material comprises the following components in parts by weight:
the polyvinyl alcohol with high polymerization degree is the polyvinyl alcohol with polymerization degree of 1799 and alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 150 and alcoholysis degree of 99%.
2. The lightweight high water absorption polyvinyl formal foam of claim 1, which is characterized by: the raw materials also comprise non-foaming pore-forming functional auxiliary agents.
3. The lightweight, high absorbency polyvinyl formal foam of claim 2, wherein: the non-foaming pore-forming functional auxiliary agent comprises any one or more of pigment and reinforcing agent.
4. The lightweight high water absorption polyvinyl formal foam of claim 1, which is characterized by: the concentration of the sulfuric acid aqueous solution is 40%.
5. The lightweight high water absorption polyvinyl formal foam of claim 1, which is characterized by: the concentration of the aqueous formaldehyde solution was 38%.
6. The lightweight high water absorption polyvinyl formal foam material according to claim 1, which is prepared by the following steps:
(1-1) preparing the following components in parts by weight:
the polyvinyl alcohol with high polymerization degree is the polyvinyl alcohol with polymerization degree of 1799 and alcoholysis degree of 99 percent;
the polyvinyl alcohol with low polymerization degree is polyvinyl alcohol with polymerization degree of 150 and alcoholysis degree of 99 percent;
(1-2) adding polyvinyl alcohol with high polymerization degree and polyvinyl alcohol with low polymerization degree into deionized water, uniformly mixing, standing for swelling for 0.5-2 h, heating to 90-95 ℃, keeping stirring for dissolving for 2-6 h, and cooling to room temperature to obtain a polyvinyl alcohol mixed solution;
and (1-3) adding a formaldehyde solution and a sulfuric acid aqueous solution into the polyvinyl alcohol mixed solution obtained in the step (1-2), uniformly mixing, heating to 70-90 ℃, reacting for 3-5 h, and after the reaction time is over, washing and drying the obtained product to obtain the open-cell PVF foam material.
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