CN107266821B - Acrylic-based emulsion copolymer surface-modified polyvinyl chloride resin and surface modification method thereof - Google Patents
Acrylic-based emulsion copolymer surface-modified polyvinyl chloride resin and surface modification method thereof Download PDFInfo
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 159
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 158
- 229920005989 resin Polymers 0.000 title claims abstract description 134
- 239000011347 resin Substances 0.000 title claims abstract description 134
- 239000000839 emulsion Substances 0.000 title claims abstract description 70
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229920001577 copolymer Polymers 0.000 title claims abstract description 66
- 238000002715 modification method Methods 0.000 title abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 21
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 239000003607 modifier Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 abstract description 24
- 239000000945 filler Substances 0.000 abstract description 17
- 238000012545 processing Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
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- 238000006116 polymerization reaction Methods 0.000 description 7
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- 229910003475 inorganic filler Inorganic materials 0.000 description 5
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- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
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- 125000000524 functional group Chemical group 0.000 description 3
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- -1 polyethylene, ethylene-vinyl acetate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QEIQEORTEYHSJH-UHFFFAOYSA-N Armin Natural products C1=CC(=O)OC2=C(O)C(OCC(CCO)C)=CC=C21 QEIQEORTEYHSJH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
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- 229920005992 thermoplastic resin Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses an acrylic acid-based emulsion copolymer surface modified polyvinyl chloride resin and a surface modification method thereof. When the polyvinyl chloride resin prepared by the surface modification method provided by the invention is used for producing the composite material, the mechanical property of the composite material can be improved, the filling amount of the filler of the composite material and the processing property of the composite material can be improved, and the production operation is simple and safe.
Description
Technical Field
The invention belongs to the technical field of polyvinyl chloride, and particularly relates to an acrylic-based emulsion copolymer surface-modified polyvinyl chloride resin and a surface modification method thereof.
Background
Polyvinyl chloride (PVC) is a versatile thermoplastic resin that is widely used, has good properties such as flame retardancy, chemical resistance, and abrasion resistance, and is inexpensive, and is widely used in the fields of construction, agriculture and industry, and packaging. However, conventional rigid polyvinyl chloride has a significant disadvantage of great brittleness, and the use of polyvinyl chloride resin as a high-performance structural material and the use of polyvinyl chloride resin as a high-filling biomass material are greatly limited due to the incompatibility of the polyvinyl chloride resin and the hydrophilic filler interface. Therefore, the toughening modification and the enhancement of the compatibility of the polyvinyl chloride resin and the filler are hot spots of the research on the modification of the polyvinyl chloride resin.
Polyvinyl chloride modification usually adopts two ways of physical blending modification and chemical polymerization modification, the latter is to graft-copolymerize functional groups in molecular chains through chemical reaction, and introduce flexible groups or other hydrophilic groups to achieve toughening or interfacial effect, but the way has the significant disadvantages of low grafting rate, complex process and high cost, for example, dipyrmingwang and the like firstly uses ACR and VC to graft-copolymerize and then utilizes ACR-g-PVC to modify PVC resin, the polymerization process is complicated, and the grafting rate in the grafting and copolymerizing process of ACR and VC is low (dipyrmingwang, stretch, Yuan Jinfeng, and the like, ACR-g-PVC composite particle structure and toughening efficiency for PVC [ J ] polymer science and report 2005(1): 47-52.), ebBoel Armin and the like, and the problem of complex polymerization process (Boebel Armin, prell Karl-Heinz, study hall repair.preparation of a shock resistant polyacrylic ester-polyvinyl-chlorinated polymer, European patent office, 0472852[ P ]. 1992-03-04.).
The physical blending modification is realized by adding a modifier in the processing process of the PVC material, and the method has the obvious advantages of simple process, convenient operation, high flexibility and the like, so the method is widely adopted by the industry, but the method is only limited to introducing another high polymer elastomer (such as chlorinated polyethylene, ethylene-vinyl acetate copolymer, MBS, APR, nitrile rubber, TPU and the like) to toughen and modify the PVC at present, but reduces the performances of the material such as rigidity, heat resistance, processing fluidity and the like to a certain extent while improving the toughness of the PVC, and cannot better improve the interfacial property of the PVC resin. For example, in the method for toughening and modifying hard polyvinyl chloride disclosed in chinese patent CN103788545B, polyvinyl chloride powder, a stabilizer, a modifier acrylate, and a graphene nanocarbon material are premixed in a high-speed mixer, then banburying is performed by a torque rheometer, then melt blending is performed by using a double-roll mill, and finally, a flat vulcanizing machine is used for hot press molding to obtain the toughened polyvinyl chloride material.
At present, the modification of polyvinyl chloride resin mainly focuses on toughening modification, and has the following main problems:
(1) functional groups are grafted into the molecular chain of the polyvinyl chloride resin through the polymerization process, but the grafting rate is low, the process is complex and the cost is high;
(2) through the physical blending process, the elastomer is mainly added for toughening, but the modification target is single, and the processing difficulty of the polyvinyl chloride resin is increased.
Disclosure of Invention
In order to solve the technical problems, the invention provides an acrylic-based emulsion copolymer surface modified polyvinyl chloride resin and a surface modification method thereof, when the polyvinyl chloride resin prepared by the surface modification method is used for producing a composite material, the mechanical property of the composite material can be improved, the filling amount of a composite material filler and the processing property of the composite material can be improved, and the production operation is simple and safe.
The technical scheme adopted by the invention is as follows:
a method for surface-modifying a polyvinyl chloride resin with an acrylic-based emulsion copolymer, comprising:
the surface of the polyvinyl chloride resin is coated with the acrylic emulsion copolymer surface modifier, and then the polyvinyl chloride resin is dried under the condition of contacting with air, so that the polyvinyl chloride resin with the acrylic emulsion copolymer surface modified is obtained.
Preferably, the surface modifier is an acrylic-based emulsion copolymer having a structure represented by formula (I):
r in the formula (I)1Selected from styrene units, vinyl acetate units, vinyl chloride units or butyl acrylate units; r2Selected from styrene units, vinyl acetate units, vinyl chloride units or butyl acrylate units; r3Is selected from-H or-CH3；R4Is selected from-H, -CH3or-CH2CH3。
Because the acrylic emulsion copolymer has strong bonding force with the hydroxyl (-OH) on the surface of the inorganic filler or the biomass fiber, the method for modifying the polyvinyl chloride resin can effectively improve the toughness and the processing performance of the polyvinyl chloride resin without complex procedures such as grafting and the like, improve the interface compatibility between the polyvinyl chloride resin and the filler, strengthen the action between the polyvinyl chloride resin and the filler and save the cost. When the modified polyvinyl chloride resin is used for processing composite products such as high-filling inorganic fillers, sectional materials, high-filling biomass fiber fillers and the like, the plasticizing performance of the polyvinyl chloride resin composite material can be improved, and simultaneously, the mechanical property of the composite material and the filling amount of the fillers are improved, so that the production can be normally operated, and the product quality is ensured.
Preferably, the amount of the surface modifier is 1 to 40 percent of the mass of the polyvinyl chloride resin.
Preferably, the amount of the surface modifier is 15 to 40 percent of the mass of the polyvinyl chloride resin.
Preferably, the method for surface modification of polyvinyl chloride resin specifically has the following three options:
the first mode is as follows: and after the polymerization of the polyvinyl chloride resin is finished, transferring the polyvinyl chloride resin into a slurry tank, adding the acrylic emulsion copolymer, uniformly mixing, filtering, and drying in a cyclone drying bed to obtain the surface-modified polyvinyl chloride resin. Wherein, preferably, the mixing time after adding the acrylic emulsion copolymer is 10-30min, and the temperature of the cyclone drying bed is 90-150 ℃.
The second mode is as follows: and after the polyvinyl chloride resin is polymerized, transferring the polyvinyl chloride resin into a slurry tank, centrifugally filtering excessive water, adding the acrylic-based emulsion copolymer, uniformly mixing, and drying in a cyclone drying bed to obtain the surface-modified polyvinyl chloride resin. Wherein, preferably, the mixing time after adding the acrylic emulsion copolymer is 10-30min, and the temperature of the cyclone drying bed is 90-150 ℃.
And in the third mode, the polyvinyl chloride resin finished product is directly added into a high-low mixer set, the surface modifier is atomized and sprayed onto the surface of the polyvinyl chloride resin under stirring, and the polyvinyl chloride resin is dried in a cyclone drying bed after being fully stirred to obtain the surface modified polyvinyl chloride resin. Preferably, the mixing rotating speed of the high-low mixer set is 200-700 rpm; the mixing temperature of the high-low mixer set is 25-60 ℃.
The invention can add the acrylic acid-based emulsion copolymer surface modifier to the surface of the polyvinyl chloride resin to modify the surface of the polyvinyl chloride resin at the slurry stage, the centrifugal filtration stage or the finished product stage of the polyvinyl chloride resin in the polymerization process of the polyvinyl chloride, and then dry the polyvinyl chloride resin coated with the acrylic acid-based emulsion copolymer surface modifier under the condition of contacting with air to obtain the acrylic acid-based emulsion copolymer surface modified polyvinyl chloride resin, thereby effectively improving the hydrophilicity and the processing performance of the polyvinyl chloride resin.
In addition, the invention also provides an acrylic emulsion copolymer surface modified polyvinyl chloride resin, which is prepared by any one of the surface modification methods.
In addition, the invention also provides application of the acrylic-based emulsion copolymer surface modified polyvinyl chloride resin in composite materials.
Compared with the prior art, the invention has the beneficial effects that: 1. according to the invention, the acrylic acid based emulsion copolymer surface modifier is added to the surface of the polyvinyl chloride resin to modify the surface of the polyvinyl chloride resin at the slurry stage, the centrifugal material stage or the finished polyvinyl chloride resin stage of the polyvinyl chloride polymerization process, and then the polyvinyl chloride resin coated with the acrylic acid based emulsion copolymer surface modifier is dried under the condition of contacting with air to obtain the acrylic acid based emulsion copolymer surface modified polyvinyl chloride resin, so that the hydrophilicity and the processability of the polyvinyl chloride resin are improved, and the preparation method is simple and easy to popularize; 2. the modified polyvinyl chloride resin is used for processing composite products such as high-filling inorganic fillers, sectional materials, high-filling biomass fiber fillers and the like, and the acrylic-based emulsion copolymer on the surface of the polyvinyl chloride resin has strong bonding force with hydroxyl (-OH) on the surface of the inorganic filler or the biomass fiber, so that the interface compatibility between the polyvinyl chloride resin and the filler is improved, the action between the polyvinyl chloride resin and the filler is enhanced, the mechanical property of the composite material is effectively improved, the filling amount of the filler is improved, the plasticizing property of the polyvinyl chloride resin is improved, and the normal operation of production is ensured.
Drawings
FIG. 1 is a graph showing the change in the thermal melting behavior of polyvinyl chloride resins modified with different kinds of surface modifiers.
FIG. 2 shows the variation of the thermal melting behavior of polyvinyl chloride resin modified by different modification processes.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An acrylic acid based emulsion copolymer surface-modified polyvinyl chloride resin, the surface modification method comprising:
1) after the polyvinyl chloride resin is polymerized, transferring the materials into a slurry tank, adding 18% of acrylic-based emulsion copolymer, and uniformly mixing for 20 min;
2) and (3) filtering excessive moisture, and transferring the material to a cyclone drying bed to be dried at 120 ℃ to obtain the polyvinyl chloride resin after the surface of the acrylic-based emulsion copolymer is modified.
Wherein the acrylic emulsion copolymer has a structure represented by formula (I):
r in the formula (I)1Is a styrene unit; r2Is a styrene unit; r3、R4Are all-H.
Example 2
A surface-modified polyvinyl chloride resin based on an acrylic emulsion copolymer, which was obtained in the same manner as in example 1, was characterized in that R in the formula (I)1Is a styrene unit; r2Is a vinyl acetate unit; r3is-H; r4Are all-CH2CH3。
Example 3
An acrylic emulsion copolymer surface-modified polyvinyl chloride resin, which was obtained by the same surface modification method as in example 1, except thatIs represented by R in formula (I)1Is a butyl acrylate unit; r2Is a vinyl acetate unit; r3、R4is-CH3。
Example 4
A surface-modified polyvinyl chloride resin based on an acrylic emulsion copolymer, which was obtained in the same manner as in example 1, was characterized in that R in the formula (I)1Is a vinyl chloride unit; r2Is a butyl acrylate unit; r4is-CH2CH3、R3is-CH3。
Example 5
A surface-modified polyvinyl chloride resin was prepared by following the procedure of example 3 except that the acrylic emulsion copolymer was added in an amount of 1%.
Example 6
A surface-modified polyvinyl chloride resin was prepared by the same procedure as in example 3, except that the acrylic emulsion copolymer was added in an amount of 40%.
Example 7
A surface-modified polyvinyl chloride resin based on an acrylic emulsion copolymer was prepared in the same manner as in example 3, except that the acrylic emulsion copolymer was added and mixed for 10 minutes at a cyclone drying bed temperature of 90 ℃.
Example 8
A surface-modified polyvinyl chloride resin based on an acrylic emulsion copolymer was prepared in the same manner as in example 3, except that the acrylic emulsion copolymer was added and mixed for 30 minutes at a cyclone drying bed temperature of 150 ℃.
Example 9
An acrylic acid based emulsion copolymer surface-modified polyvinyl chloride resin, the surface modification method comprising:
1) after the polyvinyl chloride resin is polymerized, transferring the polyvinyl chloride resin into a slurry tank, centrifugally filtering excessive water, adding 15% of acrylic-based emulsion copolymer, and uniformly mixing for 20 min;
2) and transferring the material to a cyclone drying bed to be dried at 120 ℃ to obtain the surface modified polyvinyl chloride resin.
Wherein the acrylic-based emulsion copolymer has a structure represented by formula (I):
r in the formula (I)1Is a styrene unit; r2Is a butyl acrylate unit; r3is-H, R4is-H.
Example 10
An acrylic acid based emulsion copolymer surface-modified polyvinyl chloride resin, the surface modification method comprising:
1) and (3) directly adding the polyvinyl chloride resin finished product into a high-low mixer set, and stirring at the rotating speed of 200 rpm.
2) Spraying the atomized acrylic-based emulsion copolymer (content: 35%) onto the surface of the polyvinyl chloride resin;
3) and after the acrylic emulsion copolymer is added, continuously stirring, discharging the material after the material temperature reaches 25 ℃, and drying in a cyclone drying bed to obtain the acrylic emulsion modified polyvinyl chloride resin.
Wherein the acrylic-based emulsion copolymer has a structure represented by formula (I):
r in the formula (I)1Is a vinyl acetate unit; r2Is a vinyl chloride unit; r3is-H, R4is-H.
Example 11
A surface-modified polyvinyl chloride resin based on acrylic emulsion copolymer, whose surface modification method is the same as example 10, is different in that the rotation speed of the high and low mixer set is changed to 400rpm, and the material temperature reaches 40 ℃ and then the material is discharged.
Example 12
The surface modification method of the acrylic-based emulsion copolymer surface-modified polyvinyl chloride resin is the same as that in example 10, except that the rotation speed of a high-low mixer set is changed to 700rpm, and the material temperature reaches 60 ℃ and then the material is discharged.
Comparative example 1
An unmodified polyvinyl chloride resin.
Comparative example 2
A polyvinyl chloride resin was prepared in the same manner as in example 6, except that R was1、R2、R3、R4Are all-H.
Comparative example 3
A polyvinyl chloride resin was prepared in the same manner as in example 6, except that the amount of the acrylic emulsion copolymer was changed to 50%.
Plasticizing performance test of modified polyvinyl chloride resin
The modified polyvinyl chloride resins prepared in examples 1 to 12 of the present invention and the unmodified polyvinyl chloride resin of comparative example 1 were subjected to a hot-melt behavior test, and the test results are shown in fig. 1 to 2. As can be seen from FIG. 1, examples 1, 2, 3 and 4 modified with the acrylic acid based emulsion copolymer of the present invention all showed a decrease in plasticizing torque and equilibrium torque, while advancing the completion plasticizing time; the comparative example 1 is the unmodified polyvinyl chloride resin, and the torque rheological test shows that the plasticizing peak torque and the balance torque are both higher, and the plasticizing completion time is longer; it is demonstrated that the surface modification of the polyvinyl chloride resin by the acrylic emulsion copolymer of the present invention can significantly improve the melting property of the polyvinyl chloride resin and enhance the plasticizing property of the polyvinyl chloride resin. Example 1, example 2, example 3 and example 4 are different in that the functional group R in the acrylic-based emulsion copolymer1、R2、R3、R4Different, as in example 1R1Is a styrene group having rigidity and thus has inferior plasticizing properties compared to examples 2, 3 and 4; r in example 21The vinyl acetate unit for reducing the glass transition temperature shows that the plasticizing torque and the balance torque are further reduced, and the plasticizing completion time is further advanced.
Fig. 2 is a comparison of the changes in melting behavior of PVC resin modified by different addition amounts of different acrylic-based emulsion copolymers and different surface modification methods for PVC resin, in which, for example, the addition amount of acrylic-based emulsion in example 5 is 1%, the plasticizing peak and the equilibrium torque are both high, and the time for completing plasticization is also long, and when the addition amount of the emulsion in example 6 is increased to 40%, the plasticizing peak and the equilibrium torque are greatly reduced, and plasticization is completed quickly.
Application examples of Di, acrylic acid based emulsion copolymer surface modified polyvinyl chloride resin
1. Applying acrylic-based emulsion copolymer surface modified polyvinyl chloride resin to PVC-based wood plastic with ultrahigh filling amount
The surface-modified polyvinyl chloride resins prepared in examples 1 to 12 of the invention and the polyvinyl chloride resin prepared in comparative example are respectively used in PVC-based wood plastic (floor product with the size of 170mm wide and 12mm thick and the wood fiber filling amount of 80%) with ultrahigh filling amount for trial comparison, and the surface modification effect of the acrylic-based emulsion copolymer is verified. The ultra-high loading PVC based wood-plastic formulations are listed in table 1. The processing conditions are shown in Table 2. The PVC-based wood-plastic floor with ultrahigh filling amount is GB/T245908-plus 2009 (Wood-Plastic flooring), and the detection results are shown in Table 3.
TABLE 1 application of surface modified polyvinyl chloride resin to PVC-based wood-plastic formulation with ultrahigh filling amount
TABLE 2 surface modified PVC resin applied to PVC-based wood-plastic processing technique table with ultra-high filling amount
TABLE 3 detection results of applying surface modified polyvinyl chloride resin to PVC-based wood-plastic products with ultrahigh filling amount
As can be seen from the above table, the product prepared by using the modified polyvinyl chloride resin of the embodiment of the present invention has a torsion resistance, a bending failure load, an elastic modulus, and a static bending strength that all meet the standard requirements and are superior to the products prepared in comparative examples 2 and 3, and has a strong drop hammer impact resistance at room temperature and-10 ℃, which indicates that the modified polyvinyl chloride resin of the present invention has good compatibility with hydrophilic fillers, an obvious toughening effect, and can effectively improve the mechanical properties of PVC-based wood-plastic products with ultra-high filling amount; the properties of the modified polyvinyl chloride resin prepared in example 10 were the best, indicating that the modified polyvinyl chloride resin obtained by the modification method in example 10 had the best properties. As for comparative example 1, the processing failure of the corresponding product was mainly caused by the fact that the coupling agent was not added to the raw materials, but the unmodified polyvinyl chloride resin was not compatible with the surface hydrophilic filler.
2. Applying acrylic-based emulsion copolymer surface modified polyvinyl chloride resin to high-filling-amount calcium carbonate drainage pipe
The acrylic acid based emulsion copolymer surface modified polyvinyl chloride resins prepared in examples 1 to 12 and the unmodified polyvinyl chloride resin of comparative example 1 were used for trial comparison with a high filling amount of calcium carbonate drainage pipe, respectively, to verify the surface modification effect of the acrylic acid based emulsion copolymer. The high loading calcium carbonate drain pipe formulation is listed in table 4. The high filling amount calcium carbonate drain pipe product adopts GB/T10002.1-2006 hard polyvinyl chloride (PVC-U) pipe for water supply, and the detection results are shown in Table 5.
TABLE 4 formulation of surface modified polyvinyl chloride resin for high filling calcium carbonate drainage pipe
TABLE 5 detection results of surface-modified polyvinyl chloride resin applied to high-filling-amount calcium carbonate drainage pipe
| Polyvinyl chloride resin | High filling calcium carbonate drain pipe tensile yield strength (MPa) |
| Example 1 | 40.93 |
| Example 2 | 41.30 |
| Example 3 | 45.21 |
| Example 4 | 38.33 |
| Example 5 | 19.11 |
| Example 6 | 47.50 |
| Example 7 | 35.10 |
| Example 8 | 40.61 |
| Example 9 | 30.02 |
| Example 10 | 34.66 |
| Example 11 | 40.89 |
| Example 12 | 40.75 |
| Comparative example 1 | 18.02 |
| Comparative example 2 | 18.15 |
| Comparative example 3 | 18.53 |
From the above table, it can be seen that the tensile yield strength of the products prepared from the modified polyvinyl chloride resins of examples 1 to 12 is superior to that of the product prepared from the unmodified polyvinyl chloride resin of comparative example 1, and therefore, the modified polyvinyl chloride resin of the present invention has an obvious toughening effect on the composite material.
In conclusion, the surface of the polyvinyl chloride resin is modified by the acrylic-based emulsion copolymer, so that the compatibility of the polyvinyl chloride resin and the surface hydrophilic filler can be improved, and the plasticizing performance of the polyvinyl chloride resin is improved; the modified polyvinyl chloride resin is used for processing composite material products such as high-filling inorganic fillers, sectional materials, high-filling biomass fiber fillers and the like, can effectively improve the mechanical property and the processing property of the composite material, improves the filling amount of the fillers, and has wide application prospect.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (6)
1. A method for modifying polyvinyl chloride resin on the surface of acrylic emulsion copolymer is characterized in that the surface of the polyvinyl chloride resin is evenly coated with a surface modifier and then dried under the condition of contacting with air to obtain the surface modified polyvinyl chloride resin; the surface modifier is an acrylic-based emulsion copolymer and has a structure shown in a formula (I):
r in the formula (I)1Selected from styrene units, vinyl acetate units, vinyl chloride units or butyl acrylate units; r2Selected from styrene units, vinyl acetate units, vinyl chloride units or butyl acrylate units; r3Is selected from-H or-CH3；R4Is selected from-H, -CH3or-CH2CH3；
The usage amount of the surface modifier is 15-40% of the weight of the polyvinyl chloride resin;
the method comprises the following specific steps:
the first mode is as follows: after the polyvinyl chloride resin is polymerized, transferring the polyvinyl chloride resin into a slurry tank, adding an acrylic-based emulsion copolymer, uniformly mixing, filtering, and drying in a cyclone drying bed to obtain surface-modified polyvinyl chloride resin;
alternatively, the second mode: after the polyvinyl chloride resin is polymerized, transferring the polyvinyl chloride resin into a slurry tank, centrifugally filtering excessive water, adding an acrylic-based emulsion copolymer, uniformly mixing, and drying in a cyclone drying bed to obtain surface-modified polyvinyl chloride resin;
alternatively, the third mode: and (2) directly adding the polyvinyl chloride resin finished product into a high-low mixer set, atomizing the surface modifier under stirring, spraying the atomized surface modifier onto the surface of the polyvinyl chloride resin, fully stirring, and drying in a cyclone drying bed to obtain the surface modified polyvinyl chloride resin.
2. The method of surface modification of polyvinyl chloride resin with acrylic emulsion copolymer as claimed in claim 1, wherein in the first mode, the acrylic emulsion copolymer is added and mixed for 10-30min, and the temperature of the cyclone drying bed is 90-150 ℃.
3. The method of claim 1, wherein in the second mode, the acrylic emulsion copolymer is added and mixed for 10-30min, and the cyclone drying bed temperature is 90-150 ℃.
4. The method for surface modification of a polyvinyl chloride resin based on an acrylic emulsion copolymer as claimed in claim 1, wherein in the third mode, the mixing speed of the high and low mixer is 200 to 700rpm and the mixing temperature is 25 to 60 ℃.
5. An acrylic-based emulsion copolymer surface-modified polyvinyl chloride resin obtained by the method according to any one of claims 1 to 4.
6. Use of the acrylic acid based emulsion copolymer surface modified polyvinyl chloride resin according to claim 5 in a composite material.
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| JPH05117427A (en) * | 1991-10-30 | 1993-05-14 | Mitsubishi Kasei Vinyl Co | Agricultural vinyl chloride resin film |
| JPH0848802A (en) * | 1994-08-09 | 1996-02-20 | Achilles Corp | Vinyl chloride-based resin film for agriculture |
| JP2003047344A (en) * | 2001-08-01 | 2003-02-18 | Achilles Corp | Agricultural vinyl chloride-based resin film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101434734B (en) * | 2008-12-13 | 2011-12-28 | 中国石油化工股份有限公司 | Toughened PVC resin and preparation thereof |
| CN102746444A (en) * | 2012-08-02 | 2012-10-24 | 田岳南 | Acrylate copolymer and polyvinylchlorid (PVC) resin composition utilizing same |
| KR101342073B1 (en) * | 2012-09-21 | 2013-12-16 | 한화케미칼 주식회사 | Vinyl chloride-based copolymer resins and method for preparing the same |
| CN103467886B (en) * | 2013-09-10 | 2016-01-20 | 新疆石河子中发化工有限责任公司 | Add PVC profile and the preparation method of vinyl chloride-acrylate copolymer resins |
| KR101535943B1 (en) * | 2013-12-09 | 2015-07-10 | 한화케미칼 주식회사 | PVC-based compound composition |
| CN105218731A (en) * | 2015-10-27 | 2016-01-06 | 无锡洪汇新材料科技股份有限公司 | A kind of shock resistance type chloroethylene copolymer resin and preparation method thereof |
| CN106349411A (en) * | 2016-09-24 | 2017-01-25 | 山东日科化学股份有限公司 | Toughening modifying agent for transparent polyvinyl chloride product and high-transparency polyvinyl chloride mixture |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05117427A (en) * | 1991-10-30 | 1993-05-14 | Mitsubishi Kasei Vinyl Co | Agricultural vinyl chloride resin film |
| JPH0848802A (en) * | 1994-08-09 | 1996-02-20 | Achilles Corp | Vinyl chloride-based resin film for agriculture |
| JP2003047344A (en) * | 2001-08-01 | 2003-02-18 | Achilles Corp | Agricultural vinyl chloride-based resin film |
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Denomination of invention: A PVC resin modified by acrylic based lotion copolymer and its surface modification method Granted publication date: 20200710 Pledgee: Kunming Branch of China Minsheng Bank Co.,Ltd. Pledgor: YUNNAN ZHENGBANG TECHNOLOGY CO.,LTD. Registration number: Y2023530000069 |
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