CN107266821A - Corvic and its surface modifying method that a kind of acrylic emulsion copolymers surface is modified - Google Patents
Corvic and its surface modifying method that a kind of acrylic emulsion copolymers surface is modified Download PDFInfo
- Publication number
- CN107266821A CN107266821A CN201710599442.6A CN201710599442A CN107266821A CN 107266821 A CN107266821 A CN 107266821A CN 201710599442 A CN201710599442 A CN 201710599442A CN 107266821 A CN107266821 A CN 107266821A
- Authority
- CN
- China
- Prior art keywords
- acrylic emulsion
- corvic
- emulsion copolymers
- pvc resin
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 77
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229920001577 copolymer Polymers 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 68
- 239000011347 resin Substances 0.000 claims abstract description 68
- 238000012986 modification Methods 0.000 claims abstract description 19
- 230000004048 modification Effects 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 11
- 229920001596 poly (chlorostyrenes) Polymers 0.000 claims description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010348 incorporation Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- 150000001336 alkenes Chemical group 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 70
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 69
- 239000000945 filler Substances 0.000 abstract description 24
- 238000011068 loading method Methods 0.000 abstract description 21
- 238000012545 processing Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 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
- 230000008569 process Effects 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003542 behavioural effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- -1 haloflex Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 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
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses the Corvic and its surface modifying method being modified there is provided a kind of acrylic emulsion copolymers surface, the surface modifying method is by Corvic Surface coating acrylic emulsion copolymers, then it is dried under conditions of ingress of air, obtains the Corvic of surface modification.Made from the surface modifying method provided using the present invention during polyvinyl chloride resin production composite, the processing characteristics of composite filler loading and composite can be improved while composite materials property is improved, and production operation is simple, safety.
Description
Technical field
The invention belongs to polyvinyl chloride technical field, it is poly- that more particularly to a kind of acrylic emulsion copolymers surface is modified
Vinyl chloride resin and its surface modifying method.
Background technology
Polyvinyl chloride (PVC) is a kind of extremely extensive universal thermoplastic resin of application, with good anti-flammability, resistance to
The performances such as chemical corrosivity, wearability, and it is cheap, it is widely used in the fields such as construction industry, industrial or agricultural and packaging.So
And, conventional rigid polyvinyl chloride enbrittles big significant drawback, simultaneously because Corvic and hydrophilic filler interface
It is incompatible, thus, it is significantly limit as the use of high performance structures material, also strongly limit it biological in height filling
The use of material.Therefore, it is always polyvinyl chloride tree to Corvic toughening modifying, the compatibility for strengthening itself and filler
The focus of fat study on the modification.
It is PVC modified, two kinds of approach are generally modified using physical modification and chemical polymerization, the latter is by changing
Reaction is learned by functional groups graft copolymerization in strand, introducing flexible group or other hydrophilic radicals are so as to reach toughness reinforcing
Or the interface property effect, but there is the high significant drawback of low grafting rate, complex process, cost in the approach, and such as Pan Mingwang is first
Using after ACR and VC graft copolymerizations recycle ACR-g-PVC polyvinyl chloride resin is modified, polymerization process is more complicated, and ACR with
VC graft copolymerization process grafting rates are low, and (Pan Mingwang, Zhang Liucheng, Yuan Jinfeng wait .ACR-g-PVC composite particle structures and to PVC's
Toughening efficiency [J] macromolecule journals, 2005 (1):47-52.), a kind of ACR and the VC grafting of the announcement such as Boebel Armin are common
Poly- post-modification Corvic, there is also polymerization process complex process problem (Boebel Armin, Prell Karl-
Heinz, Sturm Herald.Preparation ofa shock resistant polyacrylic ester-
polyvinyl-chloridegraft polymer:EUROPEAN PATENT OFFICE, 0472852 [P] .1992-03-04.).
Physical modification is realized by adding modifying agent in PVC material process, and the approach has work
The remarkable advantages such as skill is simple, simple operation, flexibility height, thus it is widely used by industrial quarters, but be currently limited to introduce in addition
A kind of macromolecular elastomer (such as haloflex, ethylene-vinyl acetate copolymer, MBS, APR, nitrile rubber, TPU etc.)
Method carries out toughening modifying to polyvinyl chloride, but while PVC toughness is improved, the firm of material is but reduced to a certain extent
The performances such as degree, heat resistance, processing fluidity, while can not preferably improve Corvic interfacial characteristics.Such as Chinese patent
A kind of method for RPVC toughening modifying that CN103788545B is announced, need to be by polyvinyl chloride powder, stabilizer, modification
Agent acrylate and graphene nano carbon material are premixed in homogenizer, then carry out banburying by torque rheometer, then
Using two-roll mill melt blending, last vulcanizing press hot press forming technology obtains increasing tougheness pvc material, process
Complexity, multistage process is high temperature, and process is larger to stabilizer demand, and needs addition acrylate and graphene
Two kinds of modifying agent, cost is higher, is also unfavorable for processing.
At present, to the modification of Corvic, toughening modifying is concentrated mainly on, and there is following subject matter：
(1) by polymerization process grafting functional functional group into Corvic strand, but grafting rate is low, technique
Complicated, cost is high；
(2) by physical blending process, main addition elastomer carries out toughness reinforcing, but modified object is single, and increase polychlorostyrene
The difficulty of processing of vinyl.
The content of the invention
In order to solve the above technical problems, the present invention provides the polychlorostyrene second that a kind of acrylic emulsion copolymers surface is modified
Olefine resin and its surface modifying method, will be used for polyvinyl-chloride resin in production composite made from surface modifying method of the present invention
When, the processability of composite filler loading and composite can be improved while composite materials property is improved
Can, and production operation is simple, safety.
The technical solution adopted by the present invention is as follows：
A kind of method of acrylic emulsion copolymers surface modified PVC resin, including：
By Corvic Surface coating acrylic emulsion copolymers surface modifier, then in the bar of ingress of air
It is dried under part, obtains the Corvic of acrylic emulsion copolymers surface modification.
It is preferred that, the surface modifier is acrylic emulsion copolymers, with structure shown in formula (I)：
R in formula (I)1Selected from styrene units, vinyl acetate unit, vinylchloride units or butyl acrylate units；R2It is selected from
Styrene units, vinyl acetate unit, vinylchloride units or butyl acrylate units；R3Selected from-H or-CH3；R4Selected from-H ,-
CH3Or-CH2CH3。
Because acrylic emulsion copolymers and inorganic filler or biomass fiber surface hydroxyl (- OH) adhesion are strong, because
This uses the inventive method modified PVC resin, without complicated procedures of forming such as grafting, you can effectively improve Corvic
Toughness and processing characteristics, the interface compatibility between lifting Corvic and filler, make Corvic and filler it
Between effect enhancing, it is cost-effective.The present invention is modified used for polyvinyl-chloride resin in height filling inorganic filler, section bar, height
When filling the processing of the composite products such as biomass fiber filler, polyvinyl chloride resin material plasticizing capacity can improved
While, the mechanical property of composite and the loading of filler are improved, production is normally run and ensures product quality.
It is preferred that, the surface modifier usage amount is the 1%~40% of quality of PVC resin.
It is preferred that, the surface modifier usage amount is the 15%~40% of quality of PVC resin.
It is preferred that, the method for the surface modified PVC resin specifically has following three kinds of optional modes：
First way：Treat after the completion of PVC resin polymerization, Corvic is transferred to slurry tank, then added
Acrylic emulsion copolymers, after being well mixed, filtering is dried into cyclone drying bed, obtains the polychlorostyrene of surface modification
Vinyl.Wherein, it is preferred that incorporation time is 10-30min, cyclone drying bed temperature after acrylic emulsion copolymers are added
Spend for 90-150 DEG C.
The second way：Treat after the completion of PVC resin polymerization, Corvic is transferred to slurry tank, centrifugal filtration
After excessive moisture, add acrylic emulsion copolymers and be well mixed, be dried into cyclone drying bed, obtain surface modification
Corvic.Wherein, it is preferred that incorporation time is 10-30min after acrylic emulsion copolymers are added, whirlwind is done
Dry bed tempertaure is 90-150 DEG C.
The third mode, directly adds height batch mixing unit by Corvic finished product, under agitation, surface is modified
Corvic surface is sprayed onto after agent atomization, after being sufficiently stirred for, is dried into cyclone drying bed, obtains the polychlorostyrene of surface modification
Vinyl.It is preferred that, the height batch mixing unit batch mixing rotating speed is 200~700rpm；The height batch mixing unit batch mixing temperature
Spend for 25~60 DEG C.
Acrylic emulsion copolymers surface modifier can be passed through the slurry rank in polyvinyl chloride polymerization process by the present invention
Section, centrifugal filtration stage or Corvic finished product stage are added to Corvic surface to Corvic surface
It is modified, then under conditions of ingress of air, the polychlorostyrene second to having coated acrylic emulsion copolymers surface modifier
Olefine resin is dried, and obtains the Corvic of acrylic emulsion copolymers surface modification, effectively improves polychlorostyrene
The hydrophily and processing characteristics of vinyl.
In addition, present invention also offers the Corvic that a kind of acrylic emulsion copolymers surface is modified, by upper
Any surface method of modifying is stated to be made.
In addition, being combined present invention also offers the Corvic that the acrylic emulsion copolymers surface is modified
Application in material.
Compared with prior art, the beneficial effects of the invention are as follows：1st, the present invention can be by acrylic emulsion copolymers surface
Modifying agent is added to by the slurry stage in polyvinyl chloride polymerization process, centrifugation material stage or Corvic finished product stage
Corvic surface is modified to Corvic surface, then under conditions of ingress of air, to having coated third
The Corvic of olefin(e) acid base emulsion copolymer surface modifier is dried, and obtains acrylic emulsion copolymers surface and changes
The Corvic of property, improves the hydrophily and processing characteristics of Corvic, and preparation method is simple, it is easy to push away
Extensively；2nd, it is the present invention is modified used for polyvinyl-chloride resin in height filling inorganic filler, section bar, high filling biomass fiber filler
Deng composite product processing, due to acrylic emulsion copolymers and inorganic filler or the biomass on Corvic surface
Fiber surface hydroxyl (- OH) adhesion is strong, so as to improve the interface compatibility between Corvic and filler, makes polychlorostyrene second
Effect enhancing between olefine resin and filler, effectively increases the mechanical property of composite, improves the loading of filler, together
When improve the plasticizing capacity of Corvic, it is ensured that the normal operation of production.
Brief description of the drawings
Fig. 1 is the heat fusing Behavioral change of the Corvic using variety classes surface modifying agent.
Fig. 2 is to pass through the modified Corvic heat fusing Behavioral change of different modified techniques.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention,
All other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, belongs to this hair
The scope of bright protection.
Embodiment 1
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method includes：
1) treat after the completion of PVC resin polymerization, material is transferred to slurry tank, then add 18% acrylic breast
Liquid copolymer is well mixed, and incorporation time is 20min；
2) excessive moisture is filtered out, material is transferred to cyclone drying bed in being dried at 120 DEG C, acrylic emulsion is produced and is total to
The modified Corvic of polymer surface.
Wherein acrylic emulsion copolymers, with structure shown in formula (I)：
R in formula (I)1For styrene units；R2For styrene units；R3、R4It is-H.
Embodiment 2
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method be the same as Example 1, no
It is R in formula (I) with part1For styrene units；R2For vinyl acetate unit；R3For-H；R4It is-CH2CH3。
Embodiment 3
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method be the same as Example 1, no
It is R in formula (I) with part1For butyl acrylate units；R2For vinyl acetate unit；R3、R4For-CH3。
Embodiment 4
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method be the same as Example 1, no
It is R in formula (I) with part1For vinylchloride units；R2For butyl acrylate units；R4For-CH2CH3、R3For-CH3。
Embodiment 5
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method be the same as Example 3, no
It is that the addition of acrylic emulsion copolymers is 1% with part.
Embodiment 6
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method be the same as Example 3, no
It is that the addition of acrylic emulsion copolymers is 40% with part.
Embodiment 7
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method be the same as Example 3, no
It is after the addition of acrylic emulsion copolymers that incorporation time is 10min with part, cyclone drying bed tempertaure is 90 DEG C.
Embodiment 8
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method be the same as Example 3, no
It is after the addition of acrylic emulsion copolymers that incorporation time is 30min with part, cyclone drying bed tempertaure is 150 DEG C.
Embodiment 9
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method includes：
1) treat after the completion of PVC resin polymerization, Corvic is transferred to slurry tank, centrifugal filtration excessive moisture
Afterwards, the acrylic emulsion copolymers for adding 15% are well mixed, and incorporation time is 20min；
2) material is transferred into cyclone drying bed to be dried at 120 DEG C, obtains the Corvic of surface modification.
Wherein acrylic emulsion copolymers have structure shown in formula (I)：
R in formula (I)1For styrene units；R2For butyl acrylate units；R3For-H, R4For-H.
Embodiment 10
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method includes：
1) Corvic finished product is directly added into height batch mixing unit, to be stirred under 200rpm rotating speeds.
2) the acrylic emulsion copolymers (content 35%) of atomization are sprayed onto polyvinyl chloride olefine resin surface；
3) after the completion of acrylic emulsion copolymers are added, continue to stir, material temperature releases material after reaching 25 DEG C, into rotation
Wind drying bed dry, produce acrylic it is emulsion modified after Corvic.
Wherein acrylic emulsion copolymers have structure shown in formula (I)：
R in formula (I)1For vinyl acetate unit；R2For vinylchloride units；R3For-H, R4For-H.
Embodiment 11
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method be the same as Example 10,
Difference is height batch mixing generating unit speed being changed to 400rpm, and material temperature releases material after reaching 40 DEG C.
Embodiment 12
A kind of acrylic emulsion copolymers surface modified PVC resin, its surface modifying method be the same as Example 10,
Difference is height batch mixing generating unit speed being changed to 700rpm, and material temperature releases material after reaching 60 DEG C.
Comparative example 1
Unmodified Corvic.
Comparative example 2
A kind of Corvic, preparation method be the same as Example 6, difference is R1、R2、R3、R4It is-H.
Comparative example 3
A kind of Corvic, preparation method be the same as Example 6, difference is acrylic emulsion copolymers
Addition is changed to 50%.
First, modified PVC resin plasticizing capacity is tested
By the modified PVC resin and the unmodified polychlorostyrene second of comparative example 1 obtained by the preparation of the embodiment of the present invention 1~12
Olefine resin carries out heat fusing performance testing, and test result is shown in Fig. 1-2.As shown in Figure 1, using acrylic emulsion copolymerization of the present invention
The modified embodiment 1 of thing, embodiment 2, embodiment 3 and embodiment 4 show plasticizing moment of torsion, counter balance torque reduction, simultaneously
Fusion time is completed to shift to an earlier date；And comparative example 1 is unmodified Corvic, torque rheology test display plasticizing peak is turned round, balance
Moment of torsion is higher, and it is longer to complete fusion time；Illustrate using acrylic emulsion copolymers of the present invention to Corvic
Carry out surface modified, can obviously improve the melting characteristic of Corvic resin, improve the modeling of Corvic resin
Change performance.Embodiment 1, embodiment 2, the difference of embodiment 3 and embodiment 4 are functional group in acrylic emulsion copolymers
R1、R2、R3、R4Differ, R in such as embodiment 11For with rigid styrene group, thus compared to embodiment 2, embodiment 3
Its plasticizing capacity is poor with embodiment 4；R in embodiment 21To reduce the vinyl acetate unit of glass transition temperature, then reveal plasticizing
Moment of torsion, counter balance torque are further reduced, and are further shifted to an earlier date while completing fusion time.
Fig. 2 is different acrylic emulsion copolymers Different adding amounts, uses different surfaces method of modifying pair to polyvinyl chloride resin
Acrylic emulsion addition is 1% in the modified melting behavior change contrast of polyvinyl chloride resin, such as embodiment 5, and it plastifies peak, put down
The moment of torsion that weighs is higher, and it is also longer to complete fusion time, and emulsion addition is increased into 40% in the embodiment 6, then plastify peak,
Counter balance torque is greatly reduced, and is rapidly completed plasticizing.
2nd, the Application Example of acrylic emulsion copolymers surface modified PVC resin
1st, acrylic emulsion copolymers surface modified PVC resin is applied in the modeling of superelevation loading PVC sills
Surface modified PVC resin and comparative example Corvic difference prepared by the embodiment of the present invention 1~12
For entering in superelevation loading PVC sills modeling (size is width 170mm, thick 12mm flooring products, wood fibre loading 80%)
Row is on probation to be compared, and verifies acrylic emulsion copolymers surface modification effect.Superelevation loading PVC sills modeling formula is the institute of table 1
Enumerate.Processing technology situation is shown in Table 2.Superelevation loading PVC sills molding product uses GB/T 24508-2009《Wood-plastic floor》,
Testing result is shown in Table 3.
The surface modified PVC resin of table 1 is applied to superelevation loading PVC sills and moulds formula
The surface modified PVC resin of table 2 is applied to superelevation loading PVC sills and moulds processing technology table
The surface modified PVC resin of table 3 is applied to superelevation loading PVC sill molding product testing results
As seen from the above table, using the torsion resistance of the product obtained prepared by modified PVC resin of the embodiment of the present invention,
Fracture load by bending, modulus of elasticity, MOR meet standard requirement and better than the product prepared by comparative example 2,3, and often
Temperature and -10 DEG C of anti-drop impact abilities are strong, show that modified PVC resin of the present invention is good with hydrophilic filler intermiscibility, toughness reinforcing effect
Fruit substantially, and can effectively improve the mechanical property of superelevation loading PVC sill molding products；Wherein, embodiment 10 is modified polychlorostyrene
The prepared properties of product obtained of vinyl are optimal, show the modified polyvinyl chloride obtained using the method for modifying of embodiment 10
The performance of resin is best.Process and fail as the corresponding product of comparative example 1, mainly due to being not added with coupling agent in raw material, and not
The filler of modified PVC resin and surface hydrophilic is immiscible to be caused.
2nd, acrylic emulsion copolymers surface modified PVC resin is applied to high filler loading capacity calcium carbonate drainpipe
In
The embodiment 1-12 acrylic emulsion copolymers surface modified polyvinyl chloride trees prepared and comparative example 1 is unmodified
Corvic be respectively used to high filler loading capacity calcium carbonate drainpipe carry out it is on probation compare, verify acrylic emulsion copolymers table
Face modified effect.High filler loading capacity calcium carbonate drainpipe formula is cited by table 4.High filler loading capacity calcium carbonate drainpipe product is used
GB/T10002.1-2006《Feedwater PVC-U (PVC-U) tubing》, testing result is shown in Table 5.
The surface modified PVC resin of table 4 is formulated applied to high filler loading capacity calcium carbonate drainpipe
The surface modified PVC resin of table 5 is applied to high filler loading capacity calcium carbonate drainpipe testing result
| Corvic | High filler loading capacity calcium carbonate drainpipe tensile yield strength (MPa) |
| Embodiment 1 | 40.93 |
| Embodiment 2 | 41.30 |
| Embodiment 3 | 45.21 |
| Embodiment 4 | 38.33 |
| Embodiment 5 | 19.11 |
| Embodiment 6 | 47.50 |
| Embodiment 7 | 35.10 |
| Embodiment 8 | 40.61 |
| Embodiment 9 | 30.02 |
| Embodiment 10 | 34.66 |
| Embodiment 11 | 40.89 |
| Embodiment 12 | 40.75 |
| Comparative example 1 | 18.02 |
| Comparative example 2 | 18.15 |
| Comparative example 3 | 18.53 |
As seen from the above table, using the tensile yield of the product obtained prepared by the modified PVC resin of embodiment 1~12
Intensity is superior to the tensile yield strength of the prepared product obtained of the unmodified Corvic of comparative example 1, therefore the present invention
Modified PVC resin has obvious toughening effect to composite.
In summary, the present invention is modified by acrylic emulsion copolymers to Corvic surface, can
The intermiscibility of the filler of Corvic and surface hydrophilic is improved, the plasticizing capacity of Corvic is lifted；The present invention changes
Property it is used for polyvinyl-chloride resin in composite product processing such as height filling inorganic filler, section bar, high filling biomass fiber fillers,
The mechanical property and processing characteristics of composite can be effectively improved, the loading of filler is lifted, has broad application prospects.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. a kind of method of acrylic emulsion copolymers surface modified PVC resin, it is characterised in that including following step
Suddenly：
By Corvic coated with uniform surface modifier, then it is dried, obtains under conditions of ingress of air
The Corvic that surface is modified；The surface modifier is acrylic emulsion copolymers, with structure shown in formula (I)：
R in formula (I)1Selected from styrene units, vinyl acetate unit, vinylchloride units or butyl acrylate units；R2Selected from benzene second
Alkene unit, vinyl acetate unit, vinylchloride units or butyl acrylate units；R3Selected from-H or-CH3；R4Selected from-H ,-CH3Or-
CH2CH3。
2. the method for acrylic emulsion copolymers surface modified PVC resin according to claim 1, its feature exists
In the usage amount of the surface modifier is the 1%~40% of quality of PVC resin.
3. the method for acrylic emulsion copolymers surface modified PVC resin according to claim 1, its feature exists
In comprising the following steps that：Treat after the completion of PVC resin polymerization, Corvic is transferred to slurry tank, third is then added
Olefin(e) acid base emulsion copolymer, after being well mixed, filtering is dried into cyclone drying bed, obtains the polychlorostyrene second of surface modification
Olefine resin.
4. the method for acrylic emulsion copolymers surface modified PVC resin according to claim 3, its feature exists
In incorporation time is 10-30min after the acrylic emulsion copolymers are added, and cyclone drying bed tempertaure is 90-150 DEG C.
5. the method for acrylic emulsion copolymers surface modified PVC resin according to claim 1, its feature exists
In comprising the following steps that：Treat after the completion of PVC resin polymerization, Corvic is transferred into slurry tank, and centrifugal filtration is more
After remaining moisture, add acrylic emulsion copolymers and be well mixed, be dried into cyclone drying bed, obtain surface modification
Corvic.
6. the method for acrylic emulsion copolymers surface modified PVC resin according to claim 5, its feature exists
In incorporation time is 10-30min after the acrylic emulsion copolymers are added, and cyclone drying bed tempertaure is 90-150 DEG C.
7. the method for acrylic emulsion copolymers surface modified PVC resin according to claim 1, its feature exists
In comprising the following steps that：Corvic finished product is directly added into height batch mixing unit, under agitation, by surface modifier
Corvic surface is sprayed onto after atomization, after being sufficiently stirred for, is dried into cyclone drying bed, obtains the polychlorostyrene second of surface modification
Olefine resin.
8. the method for acrylic emulsion copolymers surface modified PVC resin according to claim 7, its feature exists
In the height batch mixing unit batch mixing rotating speed is 200~700rpm, and mixture temperature is 25~60 DEG C.
9. the Corvic that a kind of acrylic emulsion copolymers surface is modified, by any one of claim 1~8 side
Method is made.
10. described in claim 9 acrylic emulsion copolymers surface be modified Corvic in the composite should
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710599442.6A CN107266821B (en) | 2017-07-21 | 2017-07-21 | Acrylic-based emulsion copolymer surface-modified polyvinyl chloride resin and surface modification method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710599442.6A CN107266821B (en) | 2017-07-21 | 2017-07-21 | Acrylic-based emulsion copolymer surface-modified polyvinyl chloride resin and surface modification method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107266821A true CN107266821A (en) | 2017-10-20 |
| CN107266821B CN107266821B (en) | 2020-07-10 |
Family
ID=60079033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710599442.6A Active CN107266821B (en) | 2017-07-21 | 2017-07-21 | Acrylic-based emulsion copolymer surface-modified polyvinyl chloride resin and surface modification method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107266821B (en) |
Citations (10)
| 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 |
| CN101434734A (en) * | 2008-12-13 | 2009-05-20 | 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 |
| CN103467886A (en) * | 2013-09-10 | 2013-12-25 | 新疆石河子中发化工有限责任公司 | PVC (Poly Vinyl Chloride) profile added with chloroethylene-acrylate copolymer resin and preparation method thereof |
| CN103814051A (en) * | 2012-09-21 | 2014-05-21 | 韩化石油化学株式会社 | Vinyl chloride-based copolymer resin and method of preparing same |
| 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 |
| CN105764979A (en) * | 2013-12-09 | 2016-07-13 | 韩化石油化学株式会社 | Pvc-based compound composition |
| 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 |
-
2017
- 2017-07-21 CN CN201710599442.6A patent/CN107266821B/en active Active
Patent Citations (10)
| 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 |
| CN101434734A (en) * | 2008-12-13 | 2009-05-20 | 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 |
| CN103814051A (en) * | 2012-09-21 | 2014-05-21 | 韩化石油化学株式会社 | Vinyl chloride-based copolymer resin and method of preparing same |
| CN103467886A (en) * | 2013-09-10 | 2013-12-25 | 新疆石河子中发化工有限责任公司 | PVC (Poly Vinyl Chloride) profile added with chloroethylene-acrylate copolymer resin and preparation method thereof |
| CN105764979A (en) * | 2013-12-09 | 2016-07-13 | 韩化石油化学株式会社 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| 王国全: "《聚合物改性》", 31 May 2016, 中国轻工业出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107266821B (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102485790B (en) | Method for preparing SiO2/ACR nano composite material | |
| CN105778001A (en) | Method for preparing carboxyl nitrile rubber by emulsion polymerization | |
| CN105504729B (en) | Polylactic acid modified material for 3D (Three-Dimensional) printing | |
| CN101704961A (en) | Plastic processing functional auxiliary agent and preparation method thereof | |
| CN102443192B (en) | Composite plastic processing agent and preparation method thereof | |
| CN106380735B (en) | High level draining lamination tubing and preparation method thereof | |
| CN104072982A (en) | High-temperature resistant nylon and preparation method thereof | |
| JP6961830B2 (en) | A core-shell copolymer, a method for producing the same, and a thermoplastic resin composition containing the same. | |
| KR101515269B1 (en) | Acrylic copolymer latex, and method for preparing thereof | |
| CN107266821A (en) | Corvic and its surface modifying method that a kind of acrylic emulsion copolymers surface is modified | |
| JPH1112427A (en) | Acrylic rubber composition | |
| CN106188952B (en) | A kind of PVC additives for process and preparation method thereof | |
| CN110437570A (en) | A kind of multi-layer core-shell particle toughening composite material of polymethyl methacrylate and preparation method | |
| CN102372857B (en) | Processing aid used for plastic and preparation method thereof | |
| CN105419130B (en) | Impact-resistant modified toughener of polyvinyl-chloride use molecular sieve and preparation method thereof | |
| CN107201051A (en) | A kind of method of ethylene-vinyl acetate chloroethylene copolymer emulsion surface modified PVC resin | |
| KR102464782B1 (en) | Acrylic copolymer composition, method for preparing the copolymer composition and resin composition comprising the copolymer composition | |
| CN107236142A (en) | A kind of method of ethylene vinyl chloride copolymer emulsion surface modified PVC resin | |
| CN102399377B (en) | Plastic processing composite functional aid and preparation method thereof | |
| CN107177141A (en) | A kind of method of propylene chloroethylene copolymer emulsion surface modified PVC resin | |
| CN107216478A (en) | Corvic and its surface modifying method that a kind of ethylene-vinyl acetate copolymer emulsion surface is modified | |
| CN103183769B (en) | Nano-silicon dioxide modified acrylic ester class linear macromolecule polymkeric substance and method for making | |
| CN107189086A (en) | A kind of method of butyronitrile emulsion surface modified PVC resin | |
| CN103183770B (en) | Nano-titanium dioxide modified esters of acrylic acid linear macromolecule polymkeric substance and method for making | |
| KR101185688B1 (en) | Acrylic Impact Modifier with Superior Processability and Polyvinyl Chloride Comprising the Same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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 |