CN108822766B - Low-solid high-viscosity polyvinyl acetate emulsion and preparation method thereof - Google Patents
Low-solid high-viscosity polyvinyl acetate emulsion and preparation method thereof Download PDFInfo
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- CN108822766B CN108822766B CN201810564072.7A CN201810564072A CN108822766B CN 108822766 B CN108822766 B CN 108822766B CN 201810564072 A CN201810564072 A CN 201810564072A CN 108822766 B CN108822766 B CN 108822766B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J131/00—Adhesives based on 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
-
- 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
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention provides a low-solid high-viscosity polyvinyl acetate emulsion, wherein vinyl acetate and acrylic acid are used as monomer mixtures in raw materials of the emulsion, a preparation method of adding the monomer mixtures step by step is adopted on the basis of optimizing a formula, the monomer mixtures are added in the second step while stirring, and the monomer mixtures are dropwise added, so that the formula components and the preparation method are reasonably matched, the polymerization reaction is more sufficient, starch is not required to be added for thickening, the viscosity of the polyvinyl acetate emulsion can be greatly improved, and the polyvinyl acetate emulsion has stronger bonding strength.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a low-solid high-viscosity polyvinyl acetate emulsion and a preparation method thereof.
Background
The polyvinyl acetate emulsion is a water-based adhesive with a large using amount, has a flexible adhesive layer, is durable in bonding, has no organic solvent, has good bonding strength, and is widely applied to interior decoration and wood industry. With the further humanity of the environmental protection concept, the requirement of people on environmental protection is higher and higher, the domestic quality standard is also higher and higher, the contents of formaldehyde and TVOC are strictly limited, and the contents of APEO and phthalate are more limited abroad. However, the environmental protection performance of the polymerized emulsion is not high due to small and numerous manufacturers for producing the products in China, uneven technical level and low price competition. The content of formaldehyde and TVOC exceeds the ten-ring standard and even exceeds the mandatory standard of national standard. For the APEO and phthalate standards of the european union, more than several times to tens of times. Formaldehyde and TVOC have the risk of carcinogenesis, APEO has toxic effects on the environment, APEO and phthalate both have estrogen-like effects, and the hormone function of the human body is compromised. If wood and interior decoration are used with the harmful polymerized emulsion, human bodies are badly affected for a long time within a plurality of years, the health of the human bodies is seriously affected, and serious people suffer from pain.
Generally, the emulsion has a relatively low solid content, and the viscosity of the emulsion after polymerization is relatively low, generally in the range of 1000-5000mpa.s, and even below 1000mpa.s, because of the relatively low solid content and the relatively low amount of monomer used. In order to increase the viscosity and meet the requirements of users, a large amount of starch and a thickening agent are required to be added, and more starch is added by 50-100 kg/ton, so that the starch cannot increase the strength of the emulsion bonded wood, the storage stability of the product is poor, the risk of putrefaction and mildew is greatly increased, the appearance of the product is influenced, more cost is increased, the market competitiveness of the product is reduced, the environmental hazard is increased, and the environmental protection performance is reduced. However, if no starch is added, the viscosity of the emulsion is too low to meet the requirements of users.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a low-solid high-viscosity polyvinyl acetate emulsion which has high viscosity, high adhesive strength, good storage stability and environmental protection.
In order to achieve the purpose, the invention provides the following technical scheme:
a low-solid high-viscosity polyvinyl acetate emulsion comprises the following raw materials in parts by weight:
in some embodiments, the preparation method of the low-solid high-viscosity polyvinyl acetate emulsion comprises the following steps:
mixing vinyl acetate and acrylic acid to obtain a monomer mixture; and (3) uniformly mixing 20-50% of the monomer mixture with a reaction system, carrying out heat preservation reaction for a period of time, and dropwise adding the rest monomer mixture into the reaction system.
In some embodiments, the stirring speed is 40-65 rpm, and the dropwise addition is completed within 1.5-4 h.
In some embodiments, the stirring speed is 50-60 rpm, and the dropwise addition is completed within 2-3 h.
In some of these embodiments, the adjuvant comprises:
in some of these embodiments, the plasticizer is a citrate-based edible plasticizer.
The invention also aims to provide a preparation method of the low-solid high-viscosity polyvinyl acetate emulsion. The specific technical scheme is as follows:
a preparation method of low-solid high-viscosity polyvinyl acetate emulsion comprises the following steps:
(1) mixing the raw material of claim 1 with vinyl acetate and acrylic acid to obtain a monomer mixture;
(2) sequentially adding polyvinyl alcohol and a defoaming agent into water, uniformly mixing, and heating to dissolve;
(3) cooling, sequentially adding an initiator, a chelating agent, an emulsifier, a cross-linking agent, a pH regulator and 20-40% of a monomer mixture, and carrying out heat preservation reaction;
(4) dropwise adding the rest monomer mixture into the system while stirring;
(5) adding a pH regulator and a reducing agent, uniformly mixing, and carrying out heat preservation reaction; adding a plasticizer and uniformly mixing;
(6) cooling, adding the formaldehyde-free VAE copolymer emulsion, and uniformly mixing to obtain the low-solid high-viscosity polyvinyl acetate emulsion.
In some embodiments, the stirring speed in the step (4) is 40-65 rpm, and the dropwise addition is completed within 1.5-4 h.
In some embodiments, the stirring speed in the step (4) is 50-60 rpm, and the dropwise addition is completed within 2-3 h.
In some of these embodiments, the dissolving by heating of step (2) is: heating to 90-95 ℃, and preserving the heat for 1-2 hours; and (3) cooling: cooling to 70-80 ℃; the time of the heat preservation reaction is 20-40 min.
In some embodiments, the temperature reduction in step (6) is to be below 50 ℃.
Based on the technical scheme, the invention has the following beneficial effects:
according to the invention, a large amount of creative labor is provided by the inventor, vinyl acetate and acrylic acid are used as monomer mixtures in raw materials, a preparation method of adding the monomer mixtures step by step is adopted on the basis of formula optimization, the monomer mixtures are added in the second step while stirring, and the formula components and the preparation method are reasonably matched, so that the polymerization reaction is more sufficient, starch is not required to be added for thickening, the viscosity of the polyvinyl acetate emulsion can be greatly improved, and the adhesive strength is stronger.
The invention further optimizes the stirring speed when the monomer mixture is dropwise added while stirring, controls the dropwise adding time, ensures that the particle size of the emulsion is in a proper range and the polymerization speed is moderate under the coordination of the two parameters, avoids the problem of emulsion viscosity reduction caused by over-small particle size of the emulsion, and has better viscosity and performance of the low-solid high-viscosity polyvinyl acetate emulsion.
The emulsion prepared by the embodiment of the invention also has the characteristics of transparent adhesive film, no pollution to bonded materials, white and bright appearance, excellent corrosion resistance, difficult mildew and long quality guarantee period, and has good usability.
The preparation method is simple and easy to operate, and is suitable for large-scale production.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Examples 1 to 3
This example provides a low solid and high viscosity polyvinyl acetate emulsion prepared from the following raw materials in parts by weight, as shown in table 1.
TABLE 1
Among them, polyvinyl alcohol in the above table has a polymerization degree of 88% and an alkaline hydrolysis degree, a molecular weight of 24000 and a viscosity of about 50mpa.s, and among them, BP24 of taiwan vinpoch is preferable.
The initiator is a peroxide initiator, and in the embodiment, ammonium persulfate is selected and is of industrial grade and purchased from Shanghai Saneis reagent company, Inc.; the cross-linking agent is a hydroxy acrylate cross-linking agent, hydroxypropyl methacrylate is selected in the embodiment, and the cross-linking agent is of industrial grade; defoaming agent in this example, an aqueous defoaming agent, Haimines, type W-082; the chelating agent is ethylenediamine tetraacetate, and disodium ethylenediamine tetraacetate is selected in the embodiment; the pH regulator is bicarbonate, and sodium bicarbonate is selected in the embodiment; the emulsifier is K12 selected in this example, and the manufacturer is Shanghai white cat group; the aldehyde-free VAE copolymer emulsion is a commercial product and is purchased from BJ-807 which is an organic product in Beijing Oriental countries; the plasticizer is edible plasticizer, and triethyl citrate is preferred in the embodiment; the reducing agent is a bisulfite, and sodium bisulfite is selected in the embodiment; the preservative can be selected from CMIT/MIT, BIT or their mixture or DM402, in this embodiment DM402 is selected, and the manufacturer is Dimei, Guangzhou.
Taking the raw materials in the table 1 as raw materials, the preparation method comprises the following steps:
(1) mixing vinyl acetate and acrylic acid at normal temperature, and slightly stirring to obtain a monomer mixture;
(2) sequentially adding polyvinyl alcohol and a defoaming agent into water, uniformly mixing, heating to 90-95 ℃, and keeping the temperature for 1-2 hours;
(3) cooling to 70-80 ℃, sequentially adding an initiator, a chelating agent, a cross-linking agent, an emulsifier, a pH regulator and 20-40% of a monomer mixture, and carrying out heat preservation reaction for 20-40 min;
(4) dropwise adding the rest monomer mixture into the system while stirring, keeping the temperature for 30-50 min after dropwise adding is finished within 1.5-4 h; wherein the stirring speed is controlled to be 40-65 rpm by adjusting a frequency converter;
(5) adding a pH regulator and a reducing agent, mixing uniformly, and then preserving heat for 20-40 min; adding plasticizer triethyl citrate, and mixing uniformly;
(6) cooling to below 50 deg.C, adding antiseptic and formaldehyde-free VAE copolymer emulsion, and mixing;
(7) and cooling to below 45 ℃, filtering by 40-100 meshes after quality inspection is qualified, and packaging to obtain the product.
Wherein, the detailed process conditions and parameter settings are shown in table 2:
TABLE 2
Comparative example 1
Compared with the example 1, the components of the comparative example 1 are the same, and the preparation method of the comparative example 1 is different from the example 1 in that the step (3) of adding part of the monomer mixture is omitted in the comparative example 1, all the monomers are directly mixed and completely dripped in the step (4), the mixture is stirred at 50rpm after being mixed, and the heat preservation reaction is carried out for 50-90 min. The emulsion is bluish in color, not milky, affecting the normal milky appearance of the emulsion. The viscosity is small and the compressive shear strength is small. The results are shown in Table 3.
TABLE 3
| Item | Example 1 | Comparative example 1 |
| Appearance of the product | Milky white color | White bluish phase |
| Viscosity Pa.s (25 ℃, rotational viscometer) | 26 | 17 |
| Compressive shear strength MPa | 11.5 | 9.8 |
Comparative example 2
Comparative example 2 compared with example 1, the components were the same, the preparation method was substantially the same, and the only difference was that the stirring speed at the time of dropping the monomer mixture in step (4) of comparative example 2 was different, and the stirring speed in comparative example 2 was 85 rpm. The viscosity of the emulsion is greatly reduced. The compressive shear strength is affected by small viscosity, large fluidity and small filling property. The test results are shown in table 4.
TABLE 4
| Item | Example 1 | Comparative example 2 |
| Viscosity Pa.s (25 ℃, rotational viscometer) | 26 | 5 |
| Compressive shear strength MPa | 11.5 | 9.1 |
Comparative example 3
Comparative example 3 compared with example 1, the composition and preparation method are basically the same, and the difference is only that in the composition of comparative example 3, the used plasticizer is common dibutyl phthalate. Compared with triethyl citrate, the phthalate substance has large harm and small compression shear strength. According to regulation 1907/2006(EC), congress and council of european union, 172 items of highly interesting Substances (SVHC) were tested for chemical registration, evaluation, authorization and Restriction (REACH), the results of which are shown in table 5.
TABLE 5
| Item | Example 1 | Comparative example 3 |
| Compressive shear strength MPa | 11.5 | 10.1 |
| SVHC detection (172 items of high interest) | N.D. (not detected) | 10000mg/kg |
The polyvinyl acetate emulsions prepared in the above examples and comparative examples were tested according to the industry Standard HG/T2727-2010 polyvinyl acetate emulsion Wood adhesive, and the performance test results are shown in Table 6:
TABLE 6
As can be seen from the above table, the emulsion prepared by the invention has the harmful substance content, meets the requirements of 'technical requirement adhesive for HJ 2541-2016 environmental marking products' standard and 'detection of 172 high concern Substances (SVHC) of chemical registration, evaluation, authorization and Restriction (REACH) by regulation No. 1907/2006(EC) of European parliament and European Union council', has excellent environmental protection performance, and avoids the harm of the harmful substance to human health as much as possible.
The viscosity of the emulsion prepared in the examples 1-3 reaches more than 2 times of the industrial standard, wherein the effect of the examples 1-2 is remarkable and reaches more than 4 times of the industrial standard, and the viscosity and the compression shear strength of the emulsion are influenced because the stirring speed and the used time length of the monomer mixture dropwise added in the preparation method of the emulsion are not in the preferable range in the example 3, and the viscosity/mechanical property of the emulsion is slightly poorer than that of the emulsion prepared in the examples 1-2, but is still better than that of the comparative example. Compared with the embodiment 1, the comparative example 1 has no step of adding the monomer mixture, which influences the latex particle number and particle size of the emulsion, so the viscosity is lower and the mechanical property is poorer; comparative example 2 compared to example 1, when the monomer mixture was added, the stirring speed was too fast, resulting in too small particle size of the emulsion to achieve the desired viscosity; comparative example 3 uses harmful dibutyl phthalate, and the plasticizing effect is not as good as triethyl citrate, not only is the environment unfriendly, but also the compression shear strength is reduced.
In addition, the emulsion prepared by the embodiment of the invention has the characteristics of transparent adhesive film, no pollution to bonded materials, white and bright appearance, excellent corrosion resistance, difficult mildew and long shelf life, and has good usability.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The low-solid high-viscosity polyvinyl acetate emulsion is characterized by comprising the following raw materials in parts by weight:
the auxiliary agent comprises:
the preparation method of the low-solid high-viscosity polyvinyl acetate emulsion comprises the following steps:
(1) mixing vinyl acetate and acrylic acid to obtain a monomer mixture;
(2) sequentially adding polyvinyl alcohol and a defoaming agent into water, uniformly mixing, and heating to dissolve;
(3) cooling, sequentially adding an initiator, a chelating agent, an emulsifier, hydroxypropyl acrylate, a pH regulator and 20-40% of a monomer mixture, and carrying out heat preservation reaction;
(4) dropwise adding the rest monomer mixture into the system while stirring;
(5) adding a pH regulator and a reducing agent, uniformly mixing, and carrying out heat preservation reaction; adding a citrate plasticizer, and uniformly mixing;
(6) cooling, adding formaldehyde-free VAE copolymer emulsion, and mixing to obtain low-solid high-viscosity polyvinyl acetate emulsion;
and (4) stirring at the speed of 40-65 rpm, wherein the dropwise addition is completed within 1.5-4 h.
2. The low solid content and high viscosity polyvinyl acetate emulsion according to claim 1, wherein the stirring speed is 50 to 60rpm, and the dropwise addition is completed within 2 to 3 hours.
3. The low solid and high viscosity polyvinyl acetate emulsion according to claim 1 or 2, wherein the pH adjusting agent is sodium bicarbonate.
4. The low solid and high viscosity polyvinyl acetate emulsion according to claim 1 or 2, wherein the reducing agent is sodium sulfite.
5. The low-solid high-viscosity polyvinyl acetate emulsion according to claim 1 or 2, wherein the initiator is ammonium persulfate.
6. The low solid and high viscosity polyvinyl acetate emulsion according to claim 1 or 2, wherein the chelating agent is disodium ethylenediaminetetraacetate.
7. The low solid and high viscosity polyvinyl acetate emulsion according to claim 1 or 2, wherein the defoaming agent is an aqueous defoaming agent W-082.
8. A method for preparing a low-solid high-viscosity polyvinyl acetate emulsion according to any one of claims 1 to 7, comprising the steps of:
(1) mixing vinyl acetate and acrylic acid to obtain a monomer mixture;
(2) sequentially adding polyvinyl alcohol and a defoaming agent into water, uniformly mixing, and heating to dissolve;
(3) cooling, sequentially adding an initiator, a chelating agent, an emulsifier, hydroxypropyl acrylate, a pH regulator and 20-40% of a monomer mixture, and carrying out heat preservation reaction;
(4) dropwise adding the rest monomer mixture into the system while stirring;
(5) adding a pH regulator and a reducing agent, uniformly mixing, and carrying out heat preservation reaction; adding a citrate plasticizer, and uniformly mixing;
(6) cooling, adding formaldehyde-free VAE copolymer emulsion, and mixing to obtain low-solid high-viscosity polyvinyl acetate emulsion;
and (4) stirring at the speed of 40-65 rpm, wherein the dropwise addition is completed within 1.5-4 h.
9. The preparation method according to claim 8, wherein the stirring speed is 50 to 60rpm, and the dropwise addition is completed within 2 to 3 hours.
10. The method according to any one of claims 8 to 9, wherein the heating dissolution of step (2) is: heating to 90-95 ℃, and preserving the heat for 1-2 hours;
and (3) cooling: cooling to 70-80 ℃; the time of the heat preservation reaction is 20-40 min;
and (6) cooling to below 50 ℃.
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| CN110551461A (en) * | 2019-08-12 | 2019-12-10 | 杭州厚瑞科技有限公司 | Method for enhancing adhesive viscosity of industrial adhesive |
| CN110964463B (en) * | 2019-12-20 | 2021-07-13 | 湖南达美程智能科技股份有限公司 | Quick-drying environment-friendly glue suitable for toy book mounting process and preparation method thereof |
| CN114058295A (en) * | 2021-11-12 | 2022-02-18 | 华威粘结材料（上海）股份有限公司 | Hot-water-resistant food-grade paper straw adhesive and preparation method thereof |
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