CN113072786A - Nano calcium carbonate master batch, preparation method thereof and application of nano calcium carbonate master batch in UPVC (unplasticized polyvinyl chloride) reinforcement and toughening - Google Patents
Nano calcium carbonate master batch, preparation method thereof and application of nano calcium carbonate master batch in UPVC (unplasticized polyvinyl chloride) reinforcement and toughening Download PDFInfo
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- CN113072786A CN113072786A CN202110346139.1A CN202110346139A CN113072786A CN 113072786 A CN113072786 A CN 113072786A CN 202110346139 A CN202110346139 A CN 202110346139A CN 113072786 A CN113072786 A CN 113072786A
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- calcium carbonate
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 149
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 74
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 38
- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000002787 reinforcement Effects 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 15
- 239000000806 elastomer Substances 0.000 claims abstract description 15
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 13
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 12
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 17
- 229920002857 polybutadiene Polymers 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 claims description 8
- ZATOFRITFRPYBT-UHFFFAOYSA-N C1=CC=C2C([Li])=CC=CC2=C1 Chemical compound C1=CC=C2C([Li])=CC=CC2=C1 ZATOFRITFRPYBT-UHFFFAOYSA-N 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- ADKBGLXGTKOWIU-UHFFFAOYSA-N butanediperoxoic acid Chemical compound OOC(=O)CCC(=O)OO ADKBGLXGTKOWIU-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 22
- 239000012745 toughening agent Substances 0.000 abstract description 12
- 230000003014 reinforcing effect Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 31
- 239000003208 petroleum Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- 239000004709 Chlorinated polyethylene Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000009775 high-speed stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2427/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- 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
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a nano calcium carbonate master batch, a preparation method thereof and application of the nano calcium carbonate master batch in UPVC (unplasticized polyvinyl chloride) reinforcement and toughening. The nano calcium carbonate master batch is prepared from coating modified nano calcium carbonate, PVC resin, a calcium-zinc composite stabilizer, a polyurethane prepolymer, polytetrahydrofuran polyol, a lubricant and an ethylene-vinyl acetate copolymer elastomer, and the preparation method is very simple. The nano calcium carbonate master batch disclosed by the invention is good in compatibility with PVC, good in thermal stability, capable of effectively realizing the reinforcing, toughening and modifying of UPVC on the premise of not losing the rigidity and modulus of the material, capable of replacing traditional toughening agents such as CPE, ACR and the like, excellent in processing performance, simple in preparation process and suitable for industrial popularization and application.
Description
Technical Field
The invention relates to the technical field of plastic modification, in particular to a nano calcium carbonate master batch, a preparation method thereof and application thereof in UPVC (unplasticized polyvinyl chloride) reinforcement and toughening.
Background
The UPVC is generally called as hard polyvinyl chloride, is mainly applied to the aspects of pipes, pipe fittings, door and window profiles and the like, and has higher requirements on the strength and the toughness of the material. The toughening modification of UPVC usually uses traditional elastomers such as CPE (chlorinated polyethylene), ACR (acrylate copolymer) and the like, the addition amount is large, and the modulus of UPVC is reduced and the strength is reduced after a large amount of the elastomers are added. In order to reduce the amount of toughening agent added, researchers have developed new toughening agents, such as: CN111925612A discloses a PVC impact-resistant toughening processing aid prepared by copolymerizing PVC resin and an elastomer, which can reduce the consumption of CPE, contains a PVC-compatible phase and a CPE-compatible phase, can promote the CPE to form a network structure, improves the toughening effect, strengthens the action strength of the CPE and the PVC resin, but also loses the rigidity and modulus of the composite material while toughening, and does not fundamentally solve the problem.
Therefore, there is a need to develop a toughening modifier product which can effectively improve the impact resistance of the UPVC composite material without losing the rigidity and modulus of the material.
The foregoing merely provides background information related to the present invention and does not necessarily constitute prior art.
Disclosure of Invention
One of the purposes of the invention is to solve the problems that the existing toughening agent is large in addition amount in the UPVC composite material and affects the modulus and strength of the UPVC composite material, and provide the nano calcium carbonate master batch capable of effectively improving the impact resistance of the UPVC composite material on the premise of not losing the rigidity and modulus of the material.
The second purpose of the invention is to provide a preparation method of the nano calcium carbonate master batch.
The invention also aims to provide the application of the nano calcium carbonate master batch in UPVC (unplasticized polyvinyl chloride) reinforcement and toughening.
The technical scheme adopted by the invention is as follows:
the nanometer calcium carbonate master batch is prepared from the following components in percentage by mass:
coating modified nano calcium carbonate: 60% -70%;
PVC resin: 5% -12%;
calcium-zinc composite stabilizer: 0.3 to 0.5 percent;
polyurethane prepolymer: 5% -8%;
polytetrahydrofuran polyol: 2% -3%;
lubricant: 1% -2%;
ethylene-vinyl acetate copolymer elastomer: 10% -15%;
the coating layer of the coated modified nano calcium carbonate is obtained by carrying out polymerization reaction on liquid polybutadiene, succinic peroxide and (E) -2-butenedioic acid. The Liquid Polybutadiene (LPB) is also called low molecular polybutadiene, and is low molecular polybutadiene with the number average molecular weight of 1000-10000.
Preferably, the coated modified nano calcium carbonate is prepared by the following method:
1) dispersing liquid polybutadiene in a solvent, adding 1-naphthyl lithium, succinic acid peroxide and (E) -2-butenedioic acid, and carrying out polymerization reaction to obtain a coating material;
2) adding sodium stearate into the nano calcium carbonate suspension for activation modification, adding a coating material for coating modification, filtering, drying and crushing to obtain the coated modified nano calcium carbonate.
Preferably, the number average molecular weight of the liquid polybutadiene in the step 1) is 2000-3000.
Preferably, the solvent in the step 1) is prepared by compounding ethylene glycol diethyl ether and petroleum ether.
Preferably, the petroleum ether has a boiling range of 90 ℃ to 120 ℃.
Preferably, the amount of the 1-naphthyl lithium in the step 1) is 0.1-0.3% of the mass of the liquid polybutadiene.
Preferably, the dosage of the peroxysuccinic acid in the step 1) is 20-25% of the mass of the liquid polybutadiene.
Preferably, the amount of the (E) -2-butenedioic acid used in the step 1) is 10 to 18 percent of the mass of the liquid polybutadiene.
Preferably, the polymerization reaction in the step 1) is carried out at 60-80 ℃, and the reaction time is 4-5 h.
Preferably, the amount of the sodium stearate in the step 2) is 1-2% of the mass of the nano calcium carbonate.
Preferably, C in the sodium stearate obtained in the step 2)18The mass percentage of the acid is more than or equal to 35 percent, and the mass percentage of the unsaturated acid is less than or equal to 2 percent.
Preferably, the specific surface area of the nano calcium carbonate in the step 2) is 18m2/g～26m2/g。
Preferably, the mass concentration of the nano calcium carbonate suspension in the step 2) is 12.5-13.5%.
Preferably, the activation modification in the step 2) is carried out at 70-90 ℃, and the activation modification time is 30-45 min.
Preferably, the amount of the coating material in the step 2) is 2-4% of the mass of the nano calcium carbonate.
Preferably, the time for coating modification in the step 2) is 30-60 min.
Preferably, the number average molecular weight of the polyurethane prepolymer is 3000-5000, and the mass percentage content of NCO groups is 3.5% -4.5%.
Preferably, the number average molecular weight of the polytetrahydrofuran polyol is 1000-2000.
Preferably, the lubricant is at least one of stearic acid, sodium stearate and calcium stearate.
Preferably, the mass percentage of the vinyl acetate unit in the ethylene-vinyl acetate copolymer elastomer is 5-10%.
The preparation method of the nano calcium carbonate master batch comprises the following steps: mixing the coated modified nano calcium carbonate, the polyurethane prepolymer, the polytetrahydrofuran polyol and the ethylene-vinyl acetate copolymer elastomer, stirring, adding the PVC resin, the calcium-zinc composite stabilizer and the lubricant, stirring, transferring the materials into a double-screw extruder, and extruding and granulating to obtain the nano calcium carbonate master batch.
Preferably, the preparation method of the nano calcium carbonate master batch comprises the following steps: mixing the coated modified nano calcium carbonate, the polyurethane prepolymer, the polytetrahydrofuran polyol and the ethylene-vinyl acetate copolymer elastomer, stirring at 60-80 ℃, adding the PVC resin, the calcium-zinc composite stabilizer and the lubricant, stirring at 100-110 ℃, transferring the materials into a double-screw extruder, and extruding and granulating at 160-190 ℃ to obtain the nano calcium carbonate master batch.
The principle of the invention is as follows: the invention takes nano calcium carbonate with proper grain diameter as a core, and a special shell layer material is prepared, so that the nano calcium carbonate forms a core-shell structure, and polyurethane prepolymer and polytetrahydrofuran polyalcohol which are introduced in the process of preparing master grains can generate pre-crosslinking reaction with the shell layer material of the nano calcium carbonate, so as to promote the effective combination of the core-shell structure and a PVC base material, and form a three-dimensional network crosslinking structure, when the PVC base material is impacted by stress, the crosslinking points induce the formation of a large number of micro-cavities in the system, and the silver veins and cracks in the PVC base material are further absorbed by an elastic shell layer due to the constraint of the crosslinking points in the expanding process, so that the invention has more outstanding performance in the aspects of toughening strength and modulus, and due to the rigidity action of the inorganic nano core layer, and a continuous crosslinking network structure phase is formed in the system, therefore, the applied stress can be uniformly dispersed, and the effects of increasing the strength and the rigidity are achieved.
The invention has the beneficial effects that: the nano calcium carbonate master batch disclosed by the invention is good in compatibility with PVC, good in thermal stability, capable of effectively realizing the reinforcing, toughening and modifying of UPVC on the premise of not losing the rigidity and modulus of the material, capable of replacing traditional toughening agents such as CPE, ACR and the like, excellent in processing performance, simple in preparation process and suitable for industrial popularization and application.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
the preparation method of the nano calcium carbonate master batch comprises the following steps:
1) dispersing 100 parts by mass of liquid polybutadiene with the average molecular weight of 2000 in 456 parts by mass of ethylene glycol diethyl ether-petroleum ether mixed solvent (the volume ratio of ethylene glycol diethyl ether to petroleum ether is 4:1, the boiling range of petroleum ether is 90-120 ℃), adding 0.1 part by mass of 1-naphthyl lithium, 20 parts by mass of succinic peroxide and 12 parts by mass of (E) -2-butenedioic acid, and reacting for 5 hours at 70 ℃ to obtain a coating material;
2) 0.26 part by mass of sodium stearate (C)18The mass percentage of the acid is more than or equal to 35 percent, the mass percentage of the unsaturated acid is less than or equal to 2 percent), 100 parts of nano calcium carbonate (the specific surface area is 23.6 m) with the mass concentration of 13.0 percent is added2Activation is carried out for 40min at 80 ℃ in the suspension, 0.455 part by mass of coating material is added for 50min coating modification, and then filter pressing, drying and crushing are carried out to obtain the coating modified nano calcium carbonate;
3) adding 65 parts by mass of coated modified nano calcium carbonate into a high-speed mixer, stirring at a low speed, heating, starting high-speed stirring when the temperature is raised to 70 ℃, adding 8 parts by mass of polyurethane prepolymer (with the number average molecular weight of 5000 and the mass percentage of NCO groups of 3.5 percent), 3 parts by mass of polytetrahydrofuran polyol with the average molecular weight of 1000 and 13 parts by mass of ethylene-vinyl acetate copolymer elastomer (with the mass percentage of vinyl acetate units of 7 percent), adding 9 parts by mass of PVC SG-5 resin under the high-speed stirring state when the temperature is raised to 90 ℃, 0.5 part by mass of calcium-zinc composite stabilizer and 1.5 parts by mass of stearic acid, continuously heating and stirring at high speed until the temperature is raised to 110 ℃, discharging, standing for 12 hours, transferring the materials into a double-screw extruder, and extruding and granulating at 180 ℃ to obtain the nano calcium carbonate master batch.
Example 2:
the preparation method of the nano calcium carbonate master batch comprises the following steps:
1) dispersing 100 parts by mass of liquid polybutadiene with an average molecular weight of 2650 in 400 parts by mass of a glycol diethyl ether-petroleum ether mixed solvent (the volume ratio of the glycol diethyl ether to the petroleum ether is 4:1, the boiling range of the petroleum ether is 90-120 ℃), adding 0.2 part by mass of 1-naphthyl lithium, 25 parts by mass of succinic peroxide and 15 parts by mass of (E) -2-butenedioic acid, and reacting at 70 ℃ for 5 hours to obtain a coating material;
2) 0.264 part by mass of sodium stearate (C)18The mass percentage of the acid is more than or equal to 35 percent, the mass percentage of the unsaturated acid is less than or equal to 2 percent), 100 parts of nano calcium carbonate (the specific surface area is 25.3 m) with the mass concentration of 13.2 percent is added2Activation for 45min at 80 ℃ in the suspension, then adding 0.528 mass part of coating material, carrying out coating modification for 60min, and then carrying out filter pressing, drying and crushing to obtain the coated modified nano calcium carbonate;
3) adding 70 parts by mass of coated modified nano calcium carbonate into a high-speed mixer, stirring at a low speed, heating, starting high-speed stirring when the temperature is raised to 70 ℃, adding 8 parts by mass of polyurethane prepolymer (the number average molecular weight is 3000, the mass percentage of NCO groups is 4.5%), 3 parts by mass of polytetrahydrofuran polyol with the average molecular weight of 1000 and 12.2 parts by mass of ethylene-vinyl acetate copolymer elastomer (the mass percentage of vinyl acetate units is 7%), adding 5 parts by mass of PVC SG-5 resin under the high-speed stirring state when the temperature is raised to 90 ℃, 0.3 part by mass of calcium-zinc composite stabilizer and 1.5 parts by mass of stearic acid, continuously heating and stirring at high speed until the temperature is raised to 110 ℃, discharging, standing for 12 hours, transferring the materials into a double-screw extruder, and extruding and granulating at 180 ℃ to obtain the nano calcium carbonate master batch.
Example 3:
the preparation method of the nano calcium carbonate master batch comprises the following steps:
1) dispersing 100 parts by mass of liquid polybutadiene with an average molecular weight of 2650 in 567 parts by mass of ethylene glycol diethyl ether-petroleum ether mixed solvent (the volume ratio of ethylene glycol diethyl ether to petroleum ether is 4:1, the boiling range of petroleum ether is 90-120 ℃), adding 0.1 part by mass of 1-naphthyl lithium, 23 parts by mass of succinic peroxide and 16 parts by mass of (E) -2-butenedioic acid, and reacting at 70 ℃ for 4.5 hours to obtain a coating material;
2) 0.13 part by mass of sodium stearate (C)18The mass percentage of the acid is more than or equal to 35 percent, the mass percentage of the unsaturated acid is less than or equal to 2 percent), 100 parts of nano calcium carbonate (the specific surface area is 20.3 m) with the mass concentration of 13.0 percent is added2Activation is carried out for 30min at 80 ℃ in the suspension, 0.39 mass part of coating material is added for 40min coating modification, and then filter pressing, drying and crushing are carried out to obtain the coating modified nano calcium carbonate;
3) adding 60 parts by mass of coated modified nano calcium carbonate into a high-speed mixer, stirring at a low speed, heating, starting high-speed stirring when the temperature is raised to 70 ℃, adding 8 parts by mass of polyurethane prepolymer (the number average molecular weight is 3000, the mass percentage of NCO groups is 4.5%), 2.5 parts by mass of polytetrahydrofuran polyol with the average molecular weight of 1000 and 15 parts by mass of ethylene-vinyl acetate copolymer elastomer (the mass percentage of vinyl acetate units is 7%), adding 12 parts by mass of PVC SG-5 resin under the high-speed stirring state when the temperature is raised to 90 ℃, 0.5 part by mass of calcium-zinc composite stabilizer and 2 parts by mass of stearic acid, continuously heating and stirring at high speed until the temperature is raised to 110 ℃, discharging, standing for 12 hours, transferring the material into a double-screw extruder, and extruding and granulating at 180 ℃ to obtain the nano calcium carbonate master batch.
Example 4:
the preparation method of the nano calcium carbonate master batch comprises the following steps:
1) dispersing 100 parts by mass of liquid polybutadiene with an average molecular weight of 3000 in 567 parts by mass of ethylene glycol diethyl ether-petroleum ether mixed solvent (the volume ratio of ethylene glycol diethyl ether to petroleum ether is 4:1, the boiling range of petroleum ether is 90-120 ℃), adding 0.3 part by mass of 1-naphthyl lithium, 22 parts by mass of succinic peroxide and 18 parts by mass of (E) -2-butenedioic acid, and reacting at 70 ℃ for 4 hours to obtain a coating material;
2) 0.20 part by mass of sodium stearate (C)18The mass percentage of the acid is more than or equal to 35 percent, the mass percentage of the unsaturated acid is less than or equal to 2 percent), 100 parts of nano calcium carbonate (the specific surface area is 18.2 m) with the mass concentration of 13.1 percent is added2Activation is carried out for 30min at 80 ℃ in the suspension, 0.262 mass part of coating material is added for coating modification for 30min, and then filter pressing, drying and crushing are carried out to obtain the coating modified nano calcium carbonate;
3) adding 64 parts by mass of coated modified nano calcium carbonate into a high-speed mixer, stirring at a low speed, heating, starting high-speed stirring when the temperature is raised to 70 ℃, adding 5 parts by mass of polyurethane prepolymer (with the number average molecular weight of 5000 and the mass percentage of NCO groups of 3.5 percent), 2 parts by mass of polytetrahydrofuran polyol with the average molecular weight of 1000 and 14.6 parts by mass of ethylene-vinyl acetate copolymer elastomer (with the mass percentage of vinyl acetate units of 7 percent), adding 12 parts by mass of PVC SG-5 resin under the high-speed stirring state when the temperature is raised to 90 ℃, 0.4 part by mass of calcium-zinc composite stabilizer and 2 parts by mass of stearic acid, continuously heating and stirring at high speed until the temperature is raised to 110 ℃, discharging, standing for 12 hours, transferring the material into a double-screw extruder, and extruding and granulating at 180 ℃ to obtain the nano calcium carbonate master batch.
Comparative example 1:
a conventional toughener CPE is commercially available.
Comparative example 2:
a conventional toughening agent ACR on the market.
And (3) performance testing:
the nano calcium carbonate master batches of examples 1-4, the toughening agent CPE of comparative example 1 and the toughening agent ACR of comparative example 2 are used as toughening agents to prepare the hard PVC sample strip, and the hard PVC sample strip comprises the following components in parts by mass: 100 parts of PVC SG-5 resin, 30 parts of heavy calcium carbonate, 8 parts of toughening agent, 0.5 part of paraffin, 0.5 part of stearic acid and 3.5 parts of titanium dioxide, and then carrying out performance test on the hard PVC sample strip, wherein the test results are shown in the following table:
TABLE 1 Performance test results for rigid PVC splines
| Test items | Tensile Strength (MPa) | Flexural modulus (MPa) | Impact Strength (KJ/m)2) |
| Example 1 | 38.8 | 3106 | 57.3 |
| Example 2 | 40.9 | 3159 | 59.7 |
| Example 3 | 37.2 | 3083 | 56.2 |
| Example 4 | 36.5 | 3022 | 55.7 |
| Comparative example 1 | 32.7 | 2935 | 34.5 |
| Comparative example 2 | 31.3 | 2872 | 30.5 |
Note:
tensile strength: reference is made to "GB/T1040.2-2006 determination of tensile Properties of plastics part 2: test conditions for molded and extruded plastics "test;
flexural modulus: the test is carried out according to the' GB/T9341-;
impact strength: reference is made to "GB/T1043.1-2008 Plastic simple Beam impact determination part 1: non-instrumented impact test.
As can be seen from Table 1: the nano calcium carbonate master batch has excellent reinforcing and toughening effects on UPVC, and the influence on the rigidity and modulus of the UPVC is obviously smaller than that of commercially available toughening agents CPE and ACR.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The nanometer calcium carbonate master batch is characterized by being prepared from the following components in percentage by mass:
coating modified nano calcium carbonate: 60% -70%;
PVC resin: 5% -12%;
calcium-zinc composite stabilizer: 0.3 to 0.5 percent;
polyurethane prepolymer: 5% -8%;
polytetrahydrofuran polyol: 2% -3%;
lubricant: 1% -2%;
ethylene-vinyl acetate copolymer elastomer: 10% -15%;
the coating layer of the coated modified nano calcium carbonate is obtained by carrying out polymerization reaction on liquid polybutadiene, succinic peroxide and (E) -2-butenedioic acid.
2. The nano calcium carbonate masterbatch according to claim 1, characterized in that: the coated modified nano calcium carbonate is prepared by the following method:
1) dispersing liquid polybutadiene in a solvent, adding 1-naphthyl lithium, succinic acid peroxide and (E) -2-butenedioic acid, and carrying out polymerization reaction to obtain a coating material;
2) adding sodium stearate into the nano calcium carbonate suspension for activation modification, adding a coating material for coating modification, filtering, drying and crushing to obtain the coated modified nano calcium carbonate.
3. The nano calcium carbonate masterbatch according to claim 2, characterized in that: step 1), the consumption of the peroxysuccinic acid is 20-25% of the mass of the liquid polybutadiene; the dosage of the (E) -2-butenedioic acid in the step 1) is 10-18% of the mass of the liquid polybutadiene.
4. The nano calcium carbonate masterbatch according to claim 2, characterized in that: the specific surface area of the nano calcium carbonate in the step 2) is 18m2/g～26m2(ii)/g; the dosage of the coating material in the step 2) is 2-4% of the mass of the nano calcium carbonate.
5. The nano calcium carbonate master batch according to any one of claims 1 to 4, wherein: the number average molecular weight of the polyurethane prepolymer is 3000-5000, and the mass percentage content of NCO groups is 3.5% -4.5%.
6. The nano calcium carbonate master batch according to any one of claims 1 to 4, wherein: the number average molecular weight of the polytetrahydrofuran polyalcohol is 1000-2000.
7. The nano calcium carbonate master batch according to any one of claims 1 to 4, wherein: the lubricant is at least one of stearic acid, sodium stearate and calcium stearate.
8. The nano calcium carbonate master batch according to any one of claims 1 to 4, wherein: the mass percentage of the vinyl acetate unit in the ethylene-vinyl acetate copolymer elastomer is 5-10%.
9. The preparation method of the nano calcium carbonate master batch according to any one of claims 1 to 8, characterized by comprising the following steps: mixing the coated modified nano calcium carbonate, the polyurethane prepolymer, the polytetrahydrofuran polyol and the ethylene-vinyl acetate copolymer elastomer, stirring, adding the PVC resin, the calcium-zinc composite stabilizer and the lubricant, stirring, transferring the materials into a double-screw extruder, and extruding and granulating to obtain the nano calcium carbonate master batch.
10. The use of the nano calcium carbonate master batch of any one of claims 1 to 8 for UPVC reinforcement and toughening.
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Non-Patent Citations (2)
| Title |
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| （印度）ANILK.BHOWMICK 等: "《弹性体手册 第2版》", 31 January 2005, 中国石化出版社 * |
| 杨清芝: "《现代橡胶工艺学》", 30 June 1997, 中国石化出版社 * |
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