CN112708004B - Vinyl acetate-ethylene copolymer emulsion and preparation method thereof - Google Patents
Vinyl acetate-ethylene copolymer emulsion and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- 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
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Abstract
The invention belongs to the technical field of vinyl acetate copolymers, and particularly relates to a vinyl acetate-ethylene copolymer emulsion. The peeling strength of the vinyl acetate-ethylene copolymer emulsion is 0.338-0.387N/mm. The adhesive property of the vinyl acetate-ethylene copolymer emulsion is obviously improved.
Description
Technical Field
The invention belongs to the technical field of vinyl acetate copolymers, and particularly relates to a vinyl acetate-ethylene copolymer emulsion and a preparation method thereof.
Background
VAE emulsions (vinyl acetate-ethylene copolymer) emulsions were first commercialized in the middle 60 th century by Air Products Ins, air Products of the american Air-borne Products company, which was originally used for paper coating, latex paint and adhesives manufacture ("development of VAE emulsions", liu Gongwei et al, chinese adhesives, volume 14, 2 nd, 46 th, 31 th of publication 2005).
The vinyl acetate-ethylene copolymer emulsion is a polymer emulsion which is prepared by using vinyl acetate and ethylene as basic raw materials and adopting an emulsion polymerization method (VAE emulsion environmental protection research progress, zhang Bianhua, management and science and technology of middle and small enterprises, 2017, 8 th page 92, public day 2017, 24 th month, and VAE emulsion research progress, wang Wenting, chinese adhesive, 2010, 19 volume, 8 th page 59, and public day 2010, 08 and 31). Because of the introduction of ethylene monomer, compared with the polyvinyl acetate emulsion, the number of acetic acid groups on the molecular chain of the VAE emulsion is reduced, so that the mutual communication among macromolecules is reduced, the mobility among the molecules is increased, the interaction among the molecules is also reduced, and the macromolecule chain becomes soft; and because the ethylene monomer and the vinyl acetate monomer are copolymerized into a whole, the polymer becomes permanently plasticized, and compared with the externally added plasticizer, the defects of easy migration, easy permeation, easy volatilization and the like of the low-molecular plasticizer are overcome. Therefore, the VAE emulsion has the special properties of the VAE emulsion, such as film forming temperature, surface tension and the like, which are lower than those of the polyvinyl acetate emulsion, can bond various substrates which are difficult to bond by the polyvinyl acetate emulsion, is very stable to oxygen, ozone, ultraviolet rays and the like, and is superior to the polyvinyl acetate emulsion in water resistance, alkali resistance, freeze thawing resistance, acid resistance, storage stability and the like (the VAE emulsion technology advances and application, yu Zhongying, modern chemical industry, volume 9, 5, page 26, publication date 1989, 12, 31). Therefore, the vinyl acetate-ethylene copolymer emulsion is widely applied to the fields of construction, building materials, cigarette glue, waterproof paint, paper products, wood, clothing, furniture, shoemaking, handbags, pressure sensitive adhesive, fabrics, carpets, paint, art processing, three-dimensional oil painting, air filters and the like ("VAE emulsion environmental protection research progress", zhang Bianhua, middle and small enterprises management and science and technology, 2017, 92, public date 2017, 04, 24, technical progress and application of VAE emulsion ", yu Zhongying, modern chemical industry, volume 9, 5, 26, public date, 1989, 12, 31, and" VAE emulsion application and market development status "in China, zhenhai, shanghai chemical industry, volume 40, 47, 2015, 08, 31).
However, the conventional vinyl acetate-ethylene copolymer emulsion has disadvantages such as poor affinity for low surface tension substrates and low adhesion because vinyl acetate is used as a main monomer. In recent years, the industries of textile, packaging, wood processing and the like in China have changed greatly, and composite materials are widely used, so that higher requirements are put on the bonding performance of adhesives. However, the conventional carboxyl-modified vinyl acetate-ethylene copolymer emulsion is poor in adhesion property, and the peel strength (peel strength means the maximum force required for wide peeling from the contact surface, specifically, the composite peel strength of polyester fabric and nonwoven fabric) is usually about 0.2N/mm, and the adhesion strength between substrates is low, so that the adhesive strength is not ideal for use in textile, packaging, wood processing and other applications.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a vinyl acetate-ethylene copolymer emulsion having excellent adhesive properties.
The parts according to the invention are parts by mass, unless otherwise specified.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the steps of preparing raw materials including monomers, an emulsifying system, an initiator, a reducing agent, a pH regulator and water, wherein the monomers comprise alcohols with 2-8 carbon atoms and more than or equal to 2 alcohol hydroxyl groups.
Further, the alcohols are 1-3 of ethylene glycol, glycerol and pentaerythritol.
Further, the alcohol is ethylene glycol or glycerol.
Further, the monomer includes a carboxylic acid monomer.
Further, the carboxylic acid monomer is acrylic acid or an acrylic acid derivative or a combination thereof.
Further, the acrylic acid derivative is methacrylic acid.
Further, the monomers also include vinyl acetate and ethylene.
Further, the monomers include 44.0 to 52.0 parts by mass of vinyl acetate, an appropriate amount of ethylene, 5.2 to 5.7 parts by mass of carboxylic acid monomer and 1.5 to 3.5 parts by mass of alcohol.
Further, the emulsifying system is a protective colloid or an emulsifier or a combination thereof.
Further, the protective colloid is one or a combination of several polyvinyl alcohols with the polymerization degree of 500-2400 and the alcoholysis degree of 88-99%.
Further, the emulsifier is octyl phenol polyoxyethylene ether with 10 or 30 ethoxy groups or a combination thereof.
Further, the initiator is a peroxide initiator.
Further, the peroxide initiator is 1-4 of hydrogen peroxide, potassium persulfate, ammonium persulfate and tert-butyl hydroperoxide.
Further, the reducing agent is 1-6 of ascorbic acid, sodium erythorbate, tartaric acid, sodium sulfite, sodium metasilicate and sodium metabisulfite.
Further, the pH regulator is 1-4 of sodium acetate, sodium bicarbonate, sodium carbonate and disodium hydrogen phosphate.
Further, the proportioning relationship is as follows in parts by mass: 49.2 to 57.7 parts of vinyl acetate, a proper amount of ethylene, 5.2 to 5.7 parts of carboxylic acid monomer, 2.4 to 3.0 parts of emulsifying system, 0.06 to 0.32 part of initiator, 0.017 to 0.13 part of reducing agent, 1.5 to 3.5 parts of alcohol, 0.04 to 0.13 part of pH regulator and 40.0 to 45.0 parts of water.
Further, the vinyl acetate-vinyl alcohol copolymer emulsion is prepared by a semi-continuous emulsion polymerization method.
Further, the preparation method comprises the following steps: raw material preparation and feeding production, wherein the feeding production process specifically comprises the following steps:
replacing the reaction kettle with inert gas, adding water and polyvinyl alcohol into the reaction kettle, sequentially adding an emulsifying agent, a reducing agent and a pH regulator, and finally adding a monomer accounting for 10% of the total amount as an initial monomer; heating and boosting after completion, and adding an initiator into the reaction kettle; when the temperature is increased to 80 ℃ and the pressure is increased to 5.0-6.0MPa, the residual monomers are started to be fed;
and after the continuous monomer is added, closing an ethylene charging switch, adding a defoaming agent and a bactericide, and finally filtering and discharging.
Further, the preparation method comprises the following steps:
A. preparation of raw materials
A1. And (3) preparing an initiator solution: adding 2.88-3.27 parts of water and 0.06-0.32 part of initiator into an initiator tank, stirring and dissolving to prepare an initiator solution with the mass fraction of 1.8% -10%;
A2. preparing a polyvinyl alcohol solution: adding 12.6-20.7 parts of water into a dissolving tank, starting stirring, adding 1.4-2.3 parts of polyvinyl alcohol, heating to 80 ℃ until the polyvinyl alcohol is completely dissolved, and preparing a polyvinyl alcohol solution with the mass fraction of 10%;
A3. preparing a mixed monomer: adding 44.0-52.0 parts of vinyl acetate, 5.2-5.7 parts of carboxylic acid monomer and 1.5-3.5 parts of alcohol compound into a monomer tank, and uniformly stirring and mixing;
B. feeding production
3 times of replacement of the reaction kettle by nitrogen, adding water and the polyvinyl alcohol solution obtained in the step A2 into the reaction kettle, starting a stirrer, sequentially adding an emulsifying agent, a reducing agent and a pH regulator, and finally adding a mixed monomer accounting for 10% of the total amount as an initial monomer;
after completion, the temperature of the reaction materials starts to rise, and simultaneously ethylene is used for boosting the pressure of the reaction kettle system, when the pressure reaches 3.0-4.0MPa and the temperature rises to 52-76 ℃, an initiator is added into the reaction kettle at the speed of 0.6-2.4 g/min;
when the temperature of the reaction materials is increased to 80 ℃, the ethylene pressure is increased to 5.0-6.0MPa, and the residual mixed monomers are started to be fed at a speed of 5.0-6.0 g/min;
during the continuous feeding of the mixed monomers, the ethylene pressure is maintained at 5.0-6.0MPa, and the reaction temperature is controlled at 80+/-2 ℃;
closing an ethylene charging switch after the continuous monomer is added, and maintaining the reaction temperature at 80+/-2 ℃;
when the ethylene pressure is lower than 1.3MPa, the reaction is finished;
the temperature of the reaction materials is reduced to below 35 ℃, and 0.1 to 0.15 percent of defoamer and 0.1 to 0.2 percent of bactericide are added; and finally, filtering and discharging.
The invention has the beneficial effects that:
the bonding strength of the vinyl acetate-ethylene copolymer emulsion is obviously improved, the composite peeling strength of the terylene cloth and the non-woven fabric is 0.338-0.387N/mm, and the bonding between the matrixes is firm, so that the vinyl acetate-ethylene copolymer emulsion can be used for bonding in the occasions of spinning, packaging, wood processing and the like.
The vinyl acetate-ethylene copolymer emulsion has good storage stability, and the viscosity change is 4.59% -11.48% after being placed indoors for 6 months at room temperature.
The method has simple production process and is suitable for industrial production.
The vinyl acetate-ethylene copolymer emulsion disclosed by the invention has excellent adhesive property, and can meet the use requirements in the fields of wood processing, spinning, packaging, carpeting and the like.
Detailed Description
The examples are presented for better illustration of the present invention, but are not intended to limit the scope of the present invention to the examples. Those skilled in the art will appreciate that various modifications and adaptations of the embodiments described above are possible in light of the above teachings and are intended to be within the scope of the invention.
The following solid content, ethylene content, average particle diameter, dilution stability and filter residue content are detected according to the test method of corresponding indexes in the national standard of vinyl acetate-ethylene copolymer emulsion, GB/T27573-2011 vinyl acetate-ethylene copolymer emulsion;
the following viscosity is detected according to the method for testing the viscosity in the national standard of vinyl acetate-ethylene copolymer emulsion GB/T27573-2011 vinyl acetate-ethylene copolymer emulsion, the testing temperature is 25+/-0.1 ℃, and the instrument model is as follows; brookfield LVDV-II+, rotor model number 4 spindle, 60 rpm.
The following polyester fabric and non-woven fabric composite peel strength is tested according to the flexible material to flexible material test method of GB/T2791-1995 adhesive T peel strength. And selecting terylene cloth and non-woven fabric with thickness smaller than 3mm, and cutting the terylene cloth and the non-woven fabric into test pieces with length of 200mm and width of 25+/-0.5 mm. Uniformly gluing the whole width of the polyester fabric test piece, wherein the gluing length is 150mm, and the gluing amount is 12g/m 2 After finishing, the non-woven fabric test piece is aligned with the non-woven fabric test piece, and the non-woven fabric test piece is pressed by a test compound machine with the roller temperature of 160 ℃ and the pressure of 1.0 MPa. The compounded sample is placed in an environment with the temperature of 23 ℃ and the humidity of 65% for 2 hours, and then is tested by a microcomputer controlled universal tester, wherein the tester is C43 of MTS company in the United states, the testing environment temperature is 23 ℃ and the humidity is 65%, a 100N sensor is used as a testing instrument, and the width of the sample is 25mm and the thickness is 4mm. During testingThe terylene test piece and the non-woven fabric test piece are respectively clamped in an upper clamp and a lower clamp, a pulling machine is started to carry out a peeling force test at a displacement speed of 50mm/min, and when the test piece is completely peeled (the adhesive coating is damaged), the average peeling strength displayed by a microcomputer is read as the test data of the test piece. 5 sample tests were repeated for each gum sample and the average was taken as the final test data.
Example 1
The vinyl acetate-ethylene copolymer emulsion is prepared by the following steps:
A. preparation of raw materials
A1. And (3) preparing an initiator solution: 38g of deionized water and 2.7g of 27.5% hydrogen peroxide solution are added into an initiator tank, and uniformly stirred and mixed to prepare 1.8% initiator solution;
A2. preparing a polyvinyl alcohol solution: adding 207g of deionized water into a dissolution tank, starting stirring, adding 23g of polyvinyl alcohol 1788, and heating to 80 ℃ until the polyvinyl alcohol is completely dissolved;
A3. preparing a mixed monomer: 463g of vinyl acetate, 63g of acrylic acid and 21g of glycerol are added into a monomer tank, and uniformly stirred and mixed;
B. feeding production
After the reaction kettle is replaced by nitrogen for three times, 253g of deionized water and 230g of the polyvinyl alcohol solution obtained in the step A are added into the reaction kettle, a stirrer is started, then 3g of emulsifier OP-10, 1.3g of sodium erythorbate and 0.5g of sodium bicarbonate are sequentially added, and finally 52g of mixed monomer is added as an initial monomer;
heating by a jacket after completion, simultaneously boosting the reaction kettle by ethylene, and adding an initiator into the reaction kettle at a speed of 0.6g/min after the pressure reaches 3.5MPa and the temperature of reaction materials rises to 60 ℃;
when the reaction temperature was raised to 80 ℃, the ethylene pressure was raised to 5.5MPa and the remaining mixed monomer was started to be fed at a rate of 5.0 g/min;
during the continuous feeding of the mixed monomers, the ethylene pressure is maintained at 5.5MPa, and the reaction temperature is maintained at 80+/-2 ℃ by controlling the change of the feeding speed of the initiator by a computer;
closing ethylene feeding after continuous monomer feeding is completed, and controlling the feeding speed of an initiator by a computer continuously to maintain the reaction temperature at 80+/-2 ℃, and finishing the reaction when the ethylene pressure is lower than 1.3 MPa;
the temperature of the reaction materials is reduced to below 35 ℃, and 1.8g of defoamer and 2.4g of bactericide are added; and finally, filtering and discharging.
The emulsion prepared in this example was tested for solid content, ethylene content, average particle size, dilution stability, filter residue content, and viscosity, and the composite peel strength test of the polyester fabric and the nonwoven fabric was performed, and at the same time, the emulsion was left in the room for 6 months at room temperature (25.+ -. 0.5 ℃ C.) and then the viscosity of the emulsion was again tested, and the results are shown in Table 1.
Table 1 properties of the emulsion prepared in example 1
| Project | Emulsion index |
| Solid content, percent | 55.3 |
| Ethylene content% | 16.6 |
| viscosity/mPa.s | 2658 |
| Viscosity (after 6 months)/mPa.s | 2780 |
| Average particle diameter, μm | 0.897 |
| Dilution stability,% | 1.8 |
| Content of residue, ppm | 32 |
| Polyester fabric and non-woven fabric composite peeling strength/(N/mm) | 0.387 |
Example 2
The vinyl acetate-ethylene copolymer emulsion is prepared by the following steps:
A. preparation of raw materials
A1. And (3) preparing an initiator solution: 34.2g of deionized water and 3.8g of ammonium persulfate are added into an initiator tank, stirred and dissolved to prepare 10% initiator solution;
A2. preparing a polyvinyl alcohol solution: 216g of deionized water is added into a dissolution tank, stirring is started, 12g of polyvinyl alcohol 1788 and 12g of polyvinyl alcohol 1799 are added, and the temperature is raised to 85 ℃ until the polyvinyl alcohol is completely dissolved;
A3. preparing a mixed monomer: 463g of vinyl acetate, 32g of acrylic acid and 18g of pentaerythritol are added into a monomer tank, and uniformly stirred and mixed;
B. feeding production
After the reaction kettle is replaced by nitrogen for three times, 273g of deionized water and 240g of polyvinyl alcohol solution obtained in the step A2 are added into the reaction kettle, a stirrer is started, then 0.2g of sodium metasilicate, 1.2g of disodium hydrogen phosphate and 3.6g of emulsifier OP-10 are sequentially added, and finally 33g of mixed monomer is added as an initial monomer;
heating the reaction kettle by using a jacket after completion, simultaneously boosting the pressure of the reaction kettle by using ethylene, adding an initiator into the reaction kettle at a speed of 2.4g/min after the pressure reaches 3.8MPa and the temperature of the reaction material rises to 76 ℃, and stopping adding the initiator after 5 min;
when the reaction temperature began to rise and reached 80 ℃, the ethylene pressure was raised to 5.0MPa and the mixed monomer began to be fed at a rate of 5.0 g/min;
during the continuous feeding of the mixed monomers, the ethylene pressure is maintained at 5.0MPa, the feeding speed of the initiator is maintained at 0.15g/min, and the reaction temperature is maintained at 80+/-2 ℃ by means of the jacket temperature of the reaction kettle;
after the continuous monomer feeding is completed, closing an ethylene feeding switch, increasing the feeding speed of an initiator to 0.26g/min, continuously maintaining the reaction temperature at 80+/-2 ℃ by means of the jacket water temperature of the reaction kettle, and ending the reaction when the ethylene pressure is lower than 1.3 MPa;
the temperature of the reaction materials is reduced to below 35 ℃, and 1.8g of defoamer and 2.4g of bactericide are added; and finally, filtering and discharging.
The emulsion prepared in this example was tested for solid content, ethylene content, average particle size, dilution stability, filter residue content, and viscosity, and tested for composite peel strength of polyester fabric and nonwoven fabric, and at the same time, the emulsion was left in room temperature (25±0.5 ℃) for 6 months, and then the viscosity of the emulsion was again tested, and the result was shown in fig. 2.
Table 2 properties of the emulsion prepared in example 2
| Project | Emulsion index |
| Solid content, percent | 56.1 |
| Ethylene content% | 15.3 |
| viscosity/mPa.s | 3267 |
| Viscosity (after 6 months)/mPa.s | 3642 |
| Average particle diameter, μm | 0.765 |
| Dilution stability,% | 2.3 |
| Content of residue, ppm | 40 |
| Polyester fabric and non-woven fabric composite peeling strength/(N/mm) | 0.373 |
Example 3
The vinyl acetate-ethylene copolymer emulsion is prepared by the following steps:
A. preparation of raw materials
A1. And (3) preparing an initiator solution: adding 40g of deionized water and 4.4g of 30% hydrogen peroxide solution in mass fraction into an initiator tank, stirring and mixing uniformly to prepare 3.0% initiator solution in mass fraction;
A2. preparing a polyvinyl alcohol solution: 225g of deionized water is added into a dissolution tank, stirring is started, 16.67g of polyvinyl alcohol 1788 and 8.33g of polyvinyl alcohol 0588 are added, and the temperature is raised to 80 ℃ until the polyvinyl alcohol is completely dissolved;
A3. preparing a mixed monomer: 463g of vinyl acetate, 55g of acrylic acid and 28g of glycerol are added into a monomer tank, and uniformly stirred and mixed;
B. feeding production
After the reaction kettle is replaced by nitrogen for three times, 235g of deionized water and 250g of polyvinyl alcohol solution are added into the reaction kettle, then 3.1g of emulsifier OP-10 is sequentially added, a stirrer is started, then 1.4g of sodium erythorbate and 0.5g of sodium bicarbonate are added, and finally 52g of mixed monomer is added as an initial monomer;
heating by a jacket after completion, simultaneously boosting the reaction kettle by ethylene, and adding an initiator into the reaction kettle at a speed of 0.5g/min after the pressure reaches 3.5MPa and the temperature of reaction materials rises to 60 ℃;
when the reaction temperature was raised to 80℃the ethylene pressure was raised to 5.5MPa and the mixed monomers were started to be fed at a rate of 6.0 g/min. During the continuous feeding of the mixed monomers, the ethylene pressure is maintained at 5.5MPa, and the reaction temperature is maintained at 80+/-2 ℃ by controlling the change of the feeding speed of the initiator by a computer;
closing an ethylene charging switch after continuous monomer charging is finished, and continuously controlling the charging speed of an initiator by a computer to maintain the reaction temperature at 80+/-2 ℃, and finishing the reaction when the ethylene pressure is lower than 1.3 MPa;
the temperature of the reaction materials is reduced to below 35 ℃, and 1.8g of defoamer and 2.4g of bactericide are added; and finally, filtering and discharging.
The emulsion prepared in this example was tested for solid content, ethylene content, average particle size, dilution stability, filter residue content, and viscosity, and the composite peel strength test of the polyester fabric and the nonwoven fabric was performed, and at the same time, the emulsion was left in the room for 6 months at room temperature (25±0.5 ℃) and then the viscosity of the emulsion was again tested, and the result was shown in fig. 3.
TABLE 3 emulsion Properties prepared in example 3
Example 4
The vinyl acetate-ethylene copolymer emulsion is prepared by the following steps:
A. preparation of raw materials
A1. And (3) preparing an initiator solution: 38g of deionized water and 2.7g of 27.5% hydrogen peroxide solution are added into an initiator tank, and uniformly stirred and mixed to prepare 1.8% initiator solution;
A2. preparing a mixed monomer: 463g of vinyl acetate, 61g of acrylic acid and 23g of glycerol are added into a monomer tank, and uniformly stirred and mixed;
B. feeding production
After the reaction kettle is replaced by nitrogen for three times, 459g of deionized water is added into the reaction kettle, a stirrer is started, 25.0. 25.0g X-305 (octylphenol polyoxyethylene ether, the number of ethoxy groups is 30), 6.0g X-100 (octylphenol polyoxyethylene ether, the number of ethoxy groups is 10), 1.6g of sodium erythorbate and 0.5g of sodium bicarbonate are added, and finally 52g of mixed monomers are added as initial monomers;
heating by a jacket after completion, simultaneously boosting the reaction kettle by ethylene, and adding an initiator into the reaction kettle at a speed of 0.6g/min after the pressure reaches 3.4MPa and the temperature of reaction materials rises to 60 ℃;
when the reaction temperature was raised to 80 ℃, the ethylene pressure was raised to 5.5MPa and the remaining mixed monomer was started to be fed at a rate of 5.0 g/min;
during the continuous feeding of the mixed monomers, the ethylene pressure is maintained at 5.5MPa, and the reaction temperature is maintained at 80+/-2 ℃ by controlling the change of the feeding speed of the initiator by a computer;
closing ethylene feeding after continuous monomer feeding is completed, and controlling the feeding speed of an initiator by a computer continuously to maintain the reaction temperature at 80+/-2 ℃, and finishing the reaction when the ethylene pressure is lower than 1.3 MPa;
the temperature of the reaction materials is reduced to below 35 ℃, and 1.8g of defoamer and 2.4g of bactericide are added; and finally, filtering and discharging.
The emulsion prepared in this example was tested for solid content, ethylene content, average particle size, dilution stability, filter residue content, and viscosity, and tested for composite peel strength of polyester fabric and nonwoven fabric, and at the same time, the emulsion was left in room temperature (25±0.5 ℃) for 6 months, and then the viscosity of the emulsion was again tested, and the result was shown in fig. 4.
Table 4 properties of the emulsion prepared in example 4
Example 5
The vinyl acetate-ethylene copolymer emulsion is prepared by the following steps:
A. preparation of raw materials
A1. And (3) preparing an initiator solution: adding 40g of deionized water and 4.4g of 30% hydrogen peroxide solution in mass fraction into an initiator tank, stirring and mixing uniformly to prepare 3.0% initiator solution in mass fraction;
A2. preparing a polyvinyl alcohol solution: 225g of deionized water is added into a dissolution tank, stirring is started, 19.67g of polyvinyl alcohol 1788 and 5.33g of polyvinyl alcohol 1088 are added, and the temperature is raised to 80 ℃ until the polyvinyl alcohol is completely dissolved;
A3. preparing a mixed monomer: 463g of vinyl acetate, 52g of acrylic acid and 31g of ethylene glycol are added into a monomer tank, and uniformly stirred and mixed;
B. feeding production
After the reaction kettle is replaced by nitrogen for three times, 235g of deionized water and 250g of polyvinyl alcohol solution are added into the reaction kettle, then a stirrer is started, 1.3g of sodium erythorbate and 0.6g of sodium bicarbonate are added, and finally 54g of mixed monomer is added as an initial monomer;
heating by a jacket after completion, simultaneously boosting the reaction kettle by ethylene, and adding an initiator into the reaction kettle at a speed of 0.5g/min after the pressure reaches 3.7MPa and the temperature of reaction materials rises to 60 ℃;
when the reaction temperature was raised to 80℃the ethylene pressure was raised to 5.8MPa and the mixed monomers were started to be fed at a rate of 6.0 g/min. During the continuous feeding of the mixed monomers, the ethylene pressure is maintained at 5.8MPa, and the reaction temperature is maintained at 80+/-2 ℃ by controlling the change of the feeding speed of the initiator by a computer;
closing an ethylene charging switch after continuous monomer charging is finished, and continuously controlling the charging speed of an initiator by a computer to maintain the reaction temperature at 80+/-2 ℃, and finishing the reaction when the ethylene pressure is lower than 1.3 MPa;
the temperature of the reaction materials is reduced to below 35 ℃, and 1.8g of defoamer and 2.4g of bactericide are added; and finally, filtering and discharging.
The emulsion prepared in this example was tested for solid content, ethylene content, average particle size, dilution stability, filter residue content, and viscosity, and tested for composite peel strength of polyester fabric and nonwoven fabric, and at the same time, the emulsion was left in room temperature (25±0.5 ℃) for 6 months, and then the viscosity of the emulsion was again tested, and the results were shown in fig. 5.
TABLE 5 Properties of the emulsion prepared in example 5
As is clear from tables 1 to 5, the viscosity change of the vinyl acetate-ethylene copolymer emulsions prepared in examples 1 to 5 was 4.59 to 11.48% after being left in the room for 6 months at room temperature, and the composite peel strength of the polyester fabric and the nonwoven fabric was 0.338 to 0.387N/mm. The vinyl acetate-ethylene copolymer emulsion has obviously improved adhesive strength and excellent storage stability.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (12)
1. The preparation method of the vinyl acetate-ethylene copolymer emulsion is characterized by comprising the following steps:
a. Preparation of raw materials
A1 Preparing an initiator solution: adding 2.88-3.27 parts of water and 0.06-0.32 part of initiator into an initiator tank, stirring and dissolving to prepare an initiator solution with the mass fraction of 1.8% -10%;
a2 Preparing a polyvinyl alcohol solution: adding 12.6-20.7 parts of water into a dissolving tank, starting stirring, adding 1.4-2.3 parts of polyvinyl alcohol, heating to 80 ℃ until the polyvinyl alcohol is completely dissolved, and preparing a polyvinyl alcohol solution with the mass fraction of 10%;
a3 Preparing mixed monomers: adding 44.0-52.0 parts of vinyl acetate, 5.2-5.7 parts of carboxylic acid monomer and 1.5-3.5 parts of alcohol with the carbon number of 2-8 and the number of the alcoholic hydroxyl groups of more than or equal to 2 into a monomer tank, stirring and mixing uniformly;
b, feeding production
3 times of replacement of the reaction kettle by nitrogen, adding water and the polyvinyl alcohol solution obtained in the step A2 into the reaction kettle, starting a stirrer, sequentially adding an emulsifying agent, a reducing agent and a pH regulator, and finally adding a mixed monomer accounting for 10% of the total amount as an initial monomer;
after completion, the temperature of the reaction materials starts to rise, and simultaneously ethylene is used for boosting the pressure of the reaction kettle system, when the pressure reaches 3.0-4.0MPa and the temperature rises to 52-76 ℃, an initiator is added into the reaction kettle at the speed of 0.6-2.4 parts/min;
when the temperature of the reaction materials is increased to 80 ℃, the ethylene pressure is increased to 5.0-6.0MPa, and the residual mixed monomers are started to be fed at a speed of 5.0-6.0 parts/min;
during the continuous feeding of the mixed monomers, the ethylene pressure is maintained at 5.0-6.0MPa, and the reaction temperature is controlled at 80+/-2 ℃;
closing an ethylene charging switch after the continuous monomer is added, and maintaining the reaction temperature at 80+/-2 ℃;
when the ethylene pressure is lower than 1.3MPa, the reaction is finished;
the temperature of the reaction materials is reduced to below 35 ℃, and 0.1 to 0.15 percent of defoamer and 0.1 to 0.2 percent of bactericide are added; and finally, filtering and discharging.
2. The method for preparing vinyl acetate-ethylene copolymer emulsion according to claim 1, wherein the alcohols are 1 to 3 of ethylene glycol, glycerol and pentaerythritol.
3. The method for producing a vinyl acetate-ethylene copolymer emulsion according to claim 2, wherein the alcohol is ethylene glycol or glycerol.
4. A process for the preparation of a vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 3 characterised in that the carboxylic acid monomer is acrylic acid or an acrylic acid derivative or a combination thereof.
5. The method for producing a vinyl acetate-ethylene copolymer emulsion according to claim 4, wherein the acrylic acid derivative is methacrylic acid.
6. A method for preparing a vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 3, wherein the protective colloid is one or a combination of several of polyvinyl alcohols having a polymerization degree of 500 to 2400 and an alcoholysis degree of 88 to 99%.
7. The method for preparing vinyl acetate-ethylene copolymer emulsion according to claim 6, wherein the emulsifier is octyl phenol polyoxyethylene ether having 10 or 30 ethoxy groups or a combination thereof.
8. A method of preparing a vinyl acetate-ethylene copolymer emulsion according to any of claims 1 to 3 wherein the initiator is a peroxide initiator.
9. The method for preparing vinyl acetate-ethylene copolymer emulsion according to claim 8, wherein the peroxide initiator is 1 to 4 of hydrogen peroxide, potassium persulfate, ammonium persulfate and t-butyl hydroperoxide.
10. The method for preparing a vinyl acetate-ethylene copolymer emulsion according to claim 9, wherein the reducing agent is 1 to 6 of ascorbic acid, sodium erythorbate, tartaric acid, sodium sulfite, sodium metasilicate and sodium metabisulfite.
11. The method for preparing vinyl acetate-ethylene copolymer emulsion according to claim 10, wherein the pH adjustor is 1 to 4 of sodium acetate, sodium bicarbonate, sodium carbonate and disodium hydrogen phosphate.
12. A vinyl acetate-ethylene copolymer emulsion prepared according to the method of any one of claims 1 to 11.
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