CN116640392A - Impact-resistant engineering plastic and preparation method thereof - Google Patents
Impact-resistant engineering plastic and preparation method thereof Download PDFInfo
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- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 60
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 28
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 12
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 84
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000013049 sediment Substances 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000008878 coupling Effects 0.000 claims description 19
- 238000010168 coupling process Methods 0.000 claims description 19
- 238000005859 coupling reaction Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 17
- 230000029936 alkylation Effects 0.000 claims description 15
- 238000005804 alkylation reaction Methods 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- MZFGYVZYLMNXGL-UHFFFAOYSA-N undec-10-enoyl chloride Chemical compound ClC(=O)CCCCCCCCC=C MZFGYVZYLMNXGL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 230000001276 controlling effect Effects 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- BCDGQXUMWHRQCB-UHFFFAOYSA-N glycine methyl ketone Natural products CC(=O)CN BCDGQXUMWHRQCB-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 4
- 239000011147 inorganic material Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005728 strengthening Methods 0.000 abstract description 3
- 241000282376 Panthera tigris Species 0.000 abstract description 2
- 230000003139 buffering effect Effects 0.000 abstract description 2
- 230000009194 climbing Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 125000004492 methyl ester group Chemical group 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 36
- 229920000915 polyvinyl chloride Polymers 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000002895 organic esters Chemical class 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000272201 Columbiformes Species 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- 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
- C08K9/10—Encapsulated ingredients
-
- 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
-
- 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
-
- 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
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to impact-resistant engineering plastic and a preparation method thereof, and belongs to the technical field of PVC plastics. The engineering plastic comprises the following components in parts by weight: 100 parts of PVC master batch, 18-25 parts of modified impact resistant agent, 1.2-1.5 parts of lubricant, 0.5-0.8 part of accelerator, 2-3 parts of stabilizer, 0.3-0.5 part of antioxidant and 1-2 parts of carbon black; the modified impact-resistant agent takes nano calcium carbonate as a matrix, and the surface is grafted with methyl ester groups similar to a mountain climbing tiger antenna structure, so that the modified impact-resistant agent is firmly combined with PVC, the branched long-chain antenna structure has certain toughness, can timely disperse and transfer impact force when being impacted, achieves the effect of buffering and toughening, has good compatibility with the PVC matrix, forms dispersion strengthening while toughening, and has smaller influence on the strength of PVC compared with the traditional method of toughening by adding inorganic materials.
Description
Technical Field
The invention belongs to the technical field of PVC plastics, and particularly relates to impact-resistant engineering plastics and a preparation method thereof.
Background
PVC (polyvinyl chloride) building boards belong to environment-friendly products, the processing technology is very mature, the materials can be recycled, and the materials can bring better economic benefit and social effect in the aspects of promoting resource circulation, saving energy, reducing emission, economically sustainable development and the like. However, the impact resistance of PVC materials is poor, and the impact strength of pure PVC materials is only 2KJ/m 2 The left side and the right side of the device,the application of PVC materials is greatly limited.
In the prior art, the toughness is improved by mixing a certain amount of plasticizer into a PVC matrix, the application range of PVC is widened, the traditional method is to add inorganic micro powder such as ultrafine calcium carbonate and the like to form a slip toughening effect, but the strength of the PVC material is obviously reduced along with the use amount of the inorganic micro powder to a certain extent, and the impact strength of the PVC material is generally 10KJ/m 2 Left and right, difficult to further lift; along with the development of chemical industry, organic ester toughening agents such as ACR, DOTP and the like are developed in the prior art, and the compatibility of the organic ester toughening agents with a PVC matrix is improved compared with inorganic materials, however, the organic ester toughening agents are all small molecular weight ester compounds, have poor migration resistance, are easy to migrate and even precipitate in an organic solvent and high-temperature environment, so that the durability of the PVC material is not high, and the stability of engineering materials is difficult to ensure.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide impact-resistant engineering plastic and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the impact-resistant engineering plastic comprises the following components in parts by weight: 100 parts of PVC master batch, 18-25 parts of modified impact resistant agent, 1.2-1.5 parts of lubricant, 0.5-0.8 part of accelerator, 2-3 parts of stabilizer, 0.3-0.5 part of antioxidant and 1-2 parts of carbon black.
The modified impact resistant agent is prepared by the following method:
step A1: preparing an ethanol solution with the volume concentration of 40%, regulating the pH value to 8.5, adding nano calcium carbonate, performing ultrasonic dispersion for 30min at 40kHz, standing for 5h, generating a large amount of hydroxyl groups on the surface of the nano calcium carbonate in an alkaline alcohol water environment, centrifuging to obtain a bottom sediment, taking the bottom sediment as an activated matrix, mixing a silane coupling agent KH550 and deionized water, regulating the pH value to 6.0, stirring for 20min at 300rpm, hydrolyzing siloxane in the silane coupling agent KH550 into silanol in a weak acid environment, adding the activated matrix, regulating the pH value to 9.0, stirring at 600rpm for 40min at a high speed, condensing the silanol after hydrolysis with the hydroxyl groups on the surface of the nano calcium carbonate in an alkaline environment, grafting organic groups on the surface of the nano calcium carbonate, improving the compatibility with organic matters, introducing active group amino groups on the surface of the nano calcium carbonate, centrifuging again, taking the bottom sediment, placing the bottom sediment in a drying box, and drying at 60 ℃ for 1h to obtain a coupling matrix;
further, the dosage ratio of nano calcium carbonate, silane coupling agent KH550, ethanol solution and deionized water is 10g:2.8mL:70mL:40mL.
Step A2: mixing a coupling matrix, acetone and triethylamine, placing the mixture in an ice-water bath for constant temperature, stirring at 1500rpm, simultaneously dropwise adding undecylenoyl chloride, controlling the dropwise adding reaction time to be 20-30min, taking triethylamine as an acid binding agent, enabling undecylenoyl chloride to react with amino grafted on the surface of the coupling matrix, introducing long-chain alkyl into the surface of nano calcium carbonate in a covalent bond form, having good compatibility with a PVC matrix, deeply embedding the nano calcium carbonate into the PVC matrix, simultaneously introducing double bonds into the outer end part, centrifuging after the reaction, taking a bottom layer precipitate, and evaporating the bottom layer precipitate under reduced pressure to dryness to obtain an alkylation matrix;
further, the ratio of the amount of the coupling matrix, acetone, triethylamine and undecylenoyl chloride was 10g:45mL:0.1-0.2mL:3.2-3.5mL.
Step A3: uniformly mixing diethanolamine, ethanol, hydroquinone and a granny catalyst, adding an alkylation matrix, carrying out ultrasonic oscillation at 28kHz for 30-50min, carrying out addition reaction on double bonds introduced on the surface of the alkylation matrix and the diethanolamine, introducing branched hydroxyl groups on the surface of nano calcium carbonate, centrifuging after the reaction is finished, washing bottom sediment with deionized water, and drying to obtain a branched matrix;
further, the dosage ratio of alkylation matrix, diethanolamine, ethanol, hydroquinone and glab catalyst was 10g:8.5-10mL:40-50mL:35mg:8-12mg.
Step A4: mixing a branched matrix, formic acid, thionyl chloride, p-toluenesulfonic acid and tetrahydrofuran, heating to 72-78 ℃, stirring at a speed of 360rpm, carrying out reflux reaction for 2-3h, centrifuging after the reaction, taking a bottom sediment, washing with absolute ethyl alcohol, and drying to obtain a modified impact resistant agent;
further, the ratio of the amount of the branched substrate, formic acid, thionyl chloride, p-toluenesulfonic acid and tetrahydrofuran used was 10g:9-12mL:1.5-2mL:0.08-0.1g:50-60mL.
Further, the lubricant is selected from polyethylene waxes.
Further, the accelerator is selected from the group consisting of accelerator T-2001.
Further, the stabilizer is selected from the group consisting of stabilizers SP-102L.
Further, the antioxidant is selected from the group consisting of antioxidants 1010.
The preparation method of the impact-resistant engineering plastic specifically comprises the following steps:
step S1: uniformly mixing the modified impact resistant agent, the lubricant, the accelerator, the stabilizer, the antioxidant and the carbon black to obtain a composite auxiliary agent;
step S2: when the PVC master batch is heated to 120 ℃, controlling the shearing rate to 1200rpm, adding a composite additive, continuously heating to 150-165 ℃ and mixing at a high speed for 15-22min, discharging the mixture into a cold mixing pot, reducing the temperature to 90 ℃, and extruding the mixture into a die by a double screw extruder to be cooled and molded to obtain the impact-resistant engineering plastic.
The invention has the beneficial effects that:
1. the invention prepares a modified impact resistant agent with a nano calcium carbonate composite structure, and the modified impact resistant agent is applied to a PVC matrix to play roles of plasticizing impact resistance and strengthening the matrix, and has an initial tensile strength of 52.7-59.1MPa and a notch impact strength of 16.9-18.7KJ/m through test 2， Compared with the existing plasticizing PVC plastic, the PVC plastic has excellent mechanical properties;
the modified impact resistant agent takes nano calcium carbonate as a matrix, active amino is introduced to the surface through silane coupling agent KH550 treatment, undecylenoyl chloride reacts with amino grafted to the surface of the coupling matrix, long-chain alkyl is introduced to the surface of the nano calcium carbonate in a covalent bond form, the modified impact resistant agent has good compatibility with the PVC matrix, the modified impact resistant agent can be deeply embedded into the PVC matrix, the modified impact resistant agent is not easy to separate out in an organic solvent and at a higher temperature, then diethanolamine and the terminal double bond of the long-chain alkyl are added, branched hydroxyl is introduced, finally methyl ester groups are formed at the terminal, the modified impact resistant agent has good compatibility with the PVC matrix, the modified impact resistant agent forms a similar structure of 'climbing tiger feeler' in the PVC matrix, the modified impact resistant agent is firmly combined with the PVC, the branched long-chain feeler structure has certain toughness, and can be dispersed and transferred in time when impacted, and the effect of buffering and toughening is achieved.
2. The nano calcium carbonate in the modified impact resistant agent is coated by the organic layer, the organic layer has good compatibility with the PVC matrix, and dispersion strengthening is formed while toughening, so that compared with the existing method for toughening by adding inorganic materials, the modified impact resistant agent has less influence on the strength of PVC.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The starting materials and reagents in the following examples all used the same batch of materials, in which:
PVC master batch is provided by Kaiki pigeon plasticizing Co-Ltd in Yuyao, and has the brand of HT-1000 and the average polymerization degree of about 1000;
the lubricant is provided by Shanghai Yanceae new material Co., ltd, and has the model of YK-0515 and the average molecular weight of about 2000;
the accelerator is provided by Shanghai Yinglou chemical industry Co., ltd, and the model is T-2001;
the stabilizer is provided by Weifang mountain road chemical Co., ltd, and the model is SP-102L;
an antioxidant selected from antioxidant 1010, available from Shanghai Reed chemical Co., ltd;
nanometer calcium carbonate provided by Jiangxi Huaming nanometer calcium carbonate limited company, the model is SPSL-1;
a granny catalyst provided by Shanghai Seiki chemical technology Co., ltd, and a second generation catalysis;
carbon black, model LI400, supplied by Tianjin Hua Yuan chemical technology Co., ltd;
the rest of the raw materials are not described as chemical pure reagents.
Examples
The embodiment prepares the impact-resistant engineering plastic, and the specific implementation process comprises the following steps:
1) Preparation of modified impact-resistant agent
a1, preparing an ethanol solution with the volume concentration of 40% by using industrial ethanol and deionized water, adding sodium hydroxide to adjust the pH value to 8.5, adding nano calcium carbonate, placing into an ultrasonic dispersing instrument, performing ultrasonic dispersion for 30min at 40kHz, standing for 5h after ultrasonic dispersion, centrifuging after standing, pouring out supernatant, and taking a bottom layer precipitate for later use;
adding a silane coupling agent KH550 and deionized water into a reaction kettle, stirring and mixing, adding hydrochloric acid to adjust the pH value to 6.0, installing a stirrer, stirring at 300rpm for 20min, adding the precipitate into the reaction kettle, adding sodium hydroxide again to adjust the pH value to 9.0, stirring at 600rpm for 40min at a high speed, centrifuging again after stirring reaction, pouring out the supernatant, taking the bottom precipitate, and then placing the precipitate into a drying oven, and drying at 60 ℃ for 1h to obtain a coupling matrix;
in the above reaction, the dosage ratio of nano calcium carbonate, silane coupling agent KH550, ethanol solution and deionized water is 10g:2.8mL:70mL:40mL, in this step, 2kg of nano calcium carbonate was used for quantification.
a2, stirring and mixing the coupling matrix, acetone and triethylamine for 5min, then placing the mixture in an ice water bath for cooling and keeping the temperature constant, setting the stirring speed to be 1500rpm, dropwise adding undecylenoyl chloride at 50mL/min, keeping stirring after dropwise adding, controlling the overall dropwise adding reaction time to be 20min, centrifuging after the reaction, taking the bottom sediment, reducing the pressure to 100Pa, heating to 40 ℃, and evaporating to dryness to obtain an alkylation matrix;
in the above reaction, the ratio of the amount of the coupling base, acetone, triethylamine and undecylenoyl chloride used was 10g:45mL:0.2mL:3.5mL, quantified in this step as 2kg of coupling matrix.
a3, adding diethanolamine, ethanol, hydroquinone and a granny catalyst into a reaction kettle, stirring and mixing for 10min, uniformly mixing the raw materials, adding an alkylation matrix, standing for 30min under 28kHz ultrasonic oscillation, centrifuging after the reaction is finished, taking out a bottom sediment, washing with deionized water, centrifuging again, taking out the sediment, standing in a drying oven, and drying at 40 ℃ for 1.5h to obtain a branched matrix;
in the above reaction, the dosage ratio of alkylation substrate, diethanolamine, ethanol, hydroquinone and glab catalyst was 10g:10mL:50mL:35mg:12mg, in this step, of 2kg of alkylated substrate.
a4, adding the branched matrix, formic acid, thionyl chloride, paratoluenesulfonic acid and tetrahydrofuran into a reaction kettle, stirring and mixing for 10min, heating to 78 ℃, stirring at 360rpm, carrying out reflux reaction for 2h, taking out the bottom sediment, washing the bottom sediment with absolute ethyl alcohol, centrifuging again, taking out the sediment, placing the sediment in a fume hood, volatilizing the absolute ethyl alcohol, and drying to obtain the modified impact resistant agent;
in the above reaction, the amount ratio of the branched substrate, formic acid, thionyl chloride, p-toluenesulfonic acid and tetrahydrofuran was 10g:12mL:2mL:0.1g:60mL, quantified in this step as 2kg branched matrix.
2) Preparation of impact-resistant engineering plastics
s1, the following raw materials are measured
PVC master batch: 10kg;
modified impact resistance agent: 1.8kg;
and (3) a lubricant: 120g;
and (3) an accelerator: 50g;
stabilizing agent: 200g;
an antioxidant: 30g;
carbon black: 100g;
s2, adding the modified impact resistant agent, the lubricant, the accelerator, the stabilizer, the antioxidant and the carbon black into a mixer, and mixing for 15min to obtain a composite additive;
and s3, adding the PVC master batch into an internal mixer, stirring and heating to 120 ℃ at 240rpm, setting the stirring speed to be 1200rpm for high-speed shearing, adding a composite additive, continuously heating to 150 ℃ for high-speed shearing and mixing for 15min, discharging the mixture into a cold mixing pot, reducing the temperature to 90 ℃, discharging the mixed melt into a bin of a conical twin-screw extruder, and extruding the mixed melt into a die for cooling and molding through the conical twin-screw extruder to obtain the impact-resistant engineering plastic.
Examples
The embodiment prepares the impact-resistant engineering plastic, and the specific implementation process comprises the following steps:
1) Preparation of modified impact-resistant agent
a1, preparing an ethanol solution with the volume concentration of 40% by using industrial ethanol and deionized water, adding sodium hydroxide to adjust the pH value to 8.5, adding nano calcium carbonate, placing into an ultrasonic dispersing instrument, performing ultrasonic dispersion for 30min at 40kHz, standing for 5h after ultrasonic dispersion, centrifuging after standing, pouring out supernatant, and taking a bottom layer precipitate for later use;
adding a silane coupling agent KH550 and deionized water into a reaction kettle, stirring and mixing, adding hydrochloric acid to adjust the pH value to 6.0, installing a stirrer, stirring at 300rpm for 20min, adding the precipitate into the reaction kettle, adding sodium hydroxide again to adjust the pH value to 9.0, stirring at 600rpm for 40min at a high speed, centrifuging again after stirring reaction, pouring out the supernatant, taking the bottom precipitate, and then placing the precipitate into a drying oven, and drying at 60 ℃ for 1h to obtain a coupling matrix;
in the above reaction, the dosage ratio of nano calcium carbonate, silane coupling agent KH550, ethanol solution and deionized water is 10g:2.8mL:70mL:40mL, in this step, 2.7kg of nano calcium carbonate was used for quantification.
a2, stirring and mixing the coupling matrix, acetone and triethylamine for 5min, then placing the mixture in an ice water bath for cooling and keeping the temperature constant, setting the stirring speed to be 1500rpm, dropwise adding undecylenoyl chloride at 50mL/min, keeping stirring after dropwise adding, controlling the overall dropwise adding reaction time to be 30min, centrifuging after the reaction, taking the bottom sediment, reducing the pressure to 100Pa, heating to 40 ℃, and evaporating to dryness to obtain an alkylation matrix;
in the above reaction, the ratio of the amount of the coupling base, acetone, triethylamine and undecylenoyl chloride used was 10g:45mL:0.1mL:3.2mL, quantified in this step as 2.7kg of coupling matrix.
a3, adding diethanolamine, ethanol, hydroquinone and a granny catalyst into a reaction kettle, stirring and mixing for 10min, uniformly mixing the raw materials, adding an alkylation matrix, standing for 50min at 28kHz ultrasonic oscillation, centrifuging after the reaction is finished, taking out a bottom sediment, washing with deionized water, centrifuging again, taking out the sediment, standing in a drying oven, and drying at 40 ℃ for 1.5h to obtain a branched matrix;
in the above reaction, the dosage ratio of alkylation substrate, diethanolamine, ethanol, hydroquinone and glab catalyst was 10g:8.5mL:40mL:35mg:8mg, in this step, of 2.7kg of alkylated substrate.
a4, adding the branched matrix, formic acid, thionyl chloride, paratoluenesulfonic acid and tetrahydrofuran into a reaction kettle, stirring and mixing for 10min, heating to 72 ℃, stirring at 360rpm, carrying out reflux reaction for 3h, taking out the bottom sediment, washing the bottom sediment with absolute ethyl alcohol, centrifuging again, taking out the sediment, placing the sediment in a fume hood, volatilizing the absolute ethyl alcohol, and drying to obtain the modified impact resistant agent;
in the above reaction, the amount ratio of the branched substrate, formic acid, thionyl chloride, p-toluenesulfonic acid and tetrahydrofuran was 10g:9mL:1.5mL:0.08g:50mL, quantified in this step as 2.7kg branched matrix.
2) Preparation of impact-resistant engineering plastics
s1, the following raw materials are measured
PVC master batch: 10kg;
modified impact resistance agent: 2.5kg;
and (3) a lubricant: 150g;
and (3) an accelerator: 80g;
stabilizing agent: 300g;
an antioxidant: 50g;
carbon black: 200g;
s2, adding the modified impact resistant agent, the lubricant, the accelerator, the stabilizer, the antioxidant and the carbon black into a mixer, and mixing for 15min to obtain a composite additive;
and s3, adding the PVC master batch into an internal mixer, stirring and heating to 120 ℃ at 240rpm, setting the stirring speed to be 1200rpm for high-speed shearing, adding a composite additive, continuously heating to 150 ℃ for high-speed shearing and mixing for 15min, discharging the mixture into a cold mixing pot, reducing the temperature to 90 ℃, discharging the mixed melt into a bin of a conical twin-screw extruder, and extruding the mixed melt into a die for cooling and molding through the conical twin-screw extruder to obtain the impact-resistant engineering plastic.
Examples
The embodiment prepares the impact-resistant engineering plastic, and the specific implementation process comprises the following steps:
1) Preparation of modified impact-resistant agent
a1, preparing an ethanol solution with the volume concentration of 40% by using industrial ethanol and deionized water, adding sodium hydroxide to adjust the pH value to 8.5, adding nano calcium carbonate, placing into an ultrasonic dispersing instrument, performing ultrasonic dispersion for 30min at 40kHz, standing for 5h after ultrasonic dispersion, centrifuging after standing, pouring out supernatant, and taking a bottom layer precipitate for later use;
adding a silane coupling agent KH550 and deionized water into a reaction kettle, stirring and mixing, adding hydrochloric acid to adjust the pH value to 6.0, installing a stirrer, stirring at 300rpm for 20min, adding the precipitate into the reaction kettle, adding sodium hydroxide again to adjust the pH value to 9.0, stirring at 600rpm for 40min at a high speed, centrifuging again after stirring reaction, pouring out the supernatant, taking the bottom precipitate, and then placing the precipitate into a drying oven, and drying at 60 ℃ for 1h to obtain a coupling matrix;
in the above reaction, the dosage ratio of nano calcium carbonate, silane coupling agent KH550, ethanol solution and deionized water is 10g:2.8mL:70mL:40mL, in this step, 2.4kg of nano calcium carbonate was used for quantification.
a2, stirring and mixing the coupling matrix, acetone and triethylamine for 5min, then placing the mixture in an ice water bath for cooling and keeping the temperature constant, setting the stirring speed to be 1500rpm, dropwise adding undecylenoyl chloride at 50mL/min, keeping stirring after dropwise adding, controlling the overall dropwise adding reaction time to be 25min, centrifuging after the reaction, taking the bottom sediment, reducing the pressure to 100Pa, heating to 40 ℃, and evaporating to dryness to obtain an alkylation matrix;
in the above reaction, the ratio of the amount of the coupling base, acetone, triethylamine and undecylenoyl chloride used was 10g:45mL:0.15mL:3.4mL, quantified in this step as 2.4kg of coupling matrix.
a3, adding diethanolamine, ethanol, hydroquinone and a granny catalyst into a reaction kettle, stirring and mixing for 10min, uniformly mixing the raw materials, adding an alkylation matrix, standing for 40min at 28kHz ultrasonic oscillation, centrifuging after the reaction is finished, taking out a bottom sediment, washing with deionized water, centrifuging again, taking out the sediment, standing in a drying oven, and drying at 40 ℃ for 1.5h to obtain a branched matrix;
in the above reaction, the dosage ratio of alkylation substrate, diethanolamine, ethanol, hydroquinone and glab catalyst was 10g:9.2mL:45mL:35mg:11mg, in this step, of 2.4kg of alkylated substrate.
a4, adding the branched matrix, formic acid, thionyl chloride, paratoluenesulfonic acid and tetrahydrofuran into a reaction kettle, stirring and mixing for 10min, heating to 75 ℃, stirring at 360rpm, carrying out reflux reaction for 2.5h, taking out the bottom sediment, washing with absolute ethyl alcohol, centrifuging again, taking out the sediment, placing the sediment in a fume hood, volatilizing the absolute ethyl alcohol, and drying to obtain the modified impact resistant agent;
in the above reaction, the amount ratio of the branched substrate, formic acid, thionyl chloride, p-toluenesulfonic acid and tetrahydrofuran was 10g:10mL:1.8mL:0.09g:55mL, quantified in this step as 2.4kg branched matrix.
2) Preparation of impact-resistant engineering plastics
s1, the following raw materials are measured
PVC master batch: 10kg;
modified impact resistance agent: 2.2kg;
and (3) a lubricant: 140g;
and (3) an accelerator: 70g;
stabilizing agent: 220g;
an antioxidant: 45g;
carbon black: 150g;
s2, adding the modified impact resistant agent, the lubricant, the accelerator, the stabilizer, the antioxidant and the carbon black into a mixer, and mixing for 15min to obtain a composite additive;
and s3, adding the PVC master batch into an internal mixer, stirring and heating to 120 ℃ at 240rpm, setting the stirring speed to be 1200rpm for high-speed shearing, adding a composite additive, continuously heating to 150 ℃ for high-speed shearing and mixing for 15min, discharging the mixture into a cold mixing pot, reducing the temperature to 90 ℃, discharging the mixed melt into a bin of a conical twin-screw extruder, and extruding the mixed melt into a die for cooling and molding through the conical twin-screw extruder to obtain the impact-resistant engineering plastic.
Comparative example 1
This comparative example is a PVC material prepared by the method provided in example 1 of chinese patent application CN 107474435B.
The materials prepared in examples 1-3 and comparative example 1 were taken and tested for performance with reference to the following criteria:
the tensile property is tested on an M-30A universal material testing machine by referring to GB/T1040.1-2018 standard sample preparation, the tensile rate is 10mm/min, the testing temperature is 15 ℃, and the humidity is 80%;
the impact performance is prepared according to GB/T16420-2006 standard sample, a notch sample with the thickness of 80 multiplied by 10 multiplied by 4mm is prepared, the notch sample is tested on a JC-25 type simple beam pendulum impact tester, the span is 60mm, and the test environment temperature is 25 ℃;
the softening temperature is tested on an XRW-300UA thermal deformation Vicat softening point temperature determinator by referring to GB/T1633-2000 standard sample preparation, and the heating rate is selected to be 50+/-5 ℃/h;
the specific test data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the engineering plastics prepared by the invention have the tensile strength of 52.7-59.1MPa, the elongation at break of 169-182% and the notch impact strength of 16.9-18.7KJ/m 2， The strength and toughness are obviously superior to those of the existing PVC material adopting inorganic materials and organic ester plasticizers, the softening temperature is 102-106 ℃, and the PVC material accords with the general construction working condition.
To test the tolerability of the samples, the materials prepared above were taken and tested as follows:
placing the sample in an ethanol solution with the volume concentration of 80%, soaking for 10d at room temperature, taking out, washing with deionized water, drying, and performing impact performance test according to the test method;
placing the sample in an aging oven (model DLRHS-504) at 60 ℃, accelerating the aging test for 30d, taking out and cooling to room temperature, and performing impact performance test according to the test method;
the specific test data are shown in table 2:
TABLE 2
As can be seen from the data in Table 2, the engineering plastic prepared by the invention has no obvious change in notch impact strength after being subjected to accelerated aging by ethanol solution and 60 ℃, and has excellent tolerance performance.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (9)
1. The impact-resistant engineering plastic is characterized by comprising the following components in parts by weight: 100 parts of PVC master batch, 18-25 parts of modified impact resistant agent, 1.2-1.5 parts of lubricant, 0.5-0.8 part of accelerator, 2-3 parts of stabilizer, 0.3-0.5 part of antioxidant and 1-2 parts of carbon black;
the modified impact resistant agent is prepared by the following method:
step A1: preparing an ethanol solution with the volume concentration of 40%, regulating the pH value to 8.5, adding nano calcium carbonate, performing ultrasonic dispersion at 40kHz for 30min, standing for 5h, centrifuging to obtain a bottom sediment, taking the bottom sediment as an activated matrix, mixing a silane coupling agent KH550 with deionized water, regulating the pH value to 6.0, stirring at 300rpm for 20min, adding the activated matrix, regulating the pH value to 9.0, stirring at 600rpm for 40min, centrifuging, and drying to obtain a coupled matrix;
step A2: mixing a coupling matrix, acetone and triethylamine, placing in an ice-water bath for constant temperature, stirring at 1500rpm, dripping undecylenoyl chloride at the same time, controlling the dripping reaction time to be 20-30min, centrifuging after the reaction, and evaporating under reduced pressure to obtain an alkylation matrix;
step A3: mixing diethanolamine, ethanol, hydroquinone and a granny catalyst, adding an alkylation matrix, ultrasonically oscillating for 30-50min at 28kHz, centrifuging after the reaction, washing with deionized water, and drying to obtain a branched matrix;
step A4: mixing the branched matrix, formic acid, thionyl chloride, p-toluenesulfonic acid and tetrahydrofuran, heating to 72-78 ℃, stirring at 360rpm, carrying out reflux reaction for 2-3h, centrifuging after the reaction, washing with absolute ethyl alcohol, and drying to obtain the modified impact resistant agent.
2. The impact resistant engineering plastic according to claim 1, wherein the dosage ratio of nano calcium carbonate, silane coupling agent KH550, ethanol solution and deionized water is 10g:2.8mL:70mL:40mL.
3. An impact resistant engineering plastic according to claim 2, wherein the coupling matrix, acetone, triethylamine and undecylenoyl chloride are used in a ratio of 10g:45mL:0.1-0.2mL:3.2-3.5mL.
4. An impact resistant engineering plastic according to claim 3, wherein the ratio of the amount of alkylated substrate, diethanolamine, ethanol, hydroquinone and glab catalyst is 10g:8.5-10mL:40-50mL:35mg:8-12mg.
5. The impact resistant engineering plastic according to claim 4, wherein the amount ratio of the branched substrate, formic acid, thionyl chloride, p-toluenesulfonic acid and tetrahydrofuran is 10g:9-12mL:1.5-2mL:0.08-0.1g:50-60mL.
6. An impact resistant engineering plastic according to claim 1, wherein the lubricant is polyethylene wax.
7. An impact resistant engineering plastic according to claim 1, wherein the accelerator is accelerator T-2001.
8. An impact resistant engineering plastic according to claim 1, wherein the stabilizer is stabilizer SP-102L.
9. The method for preparing the impact-resistant engineering plastic according to any one of claims 1 to 8, which is characterized by comprising the following steps:
step S1: uniformly mixing the modified impact resistant agent, the lubricant, the accelerator, the stabilizer, the antioxidant and the carbon black to obtain a composite auxiliary agent;
step S2: when the PVC master batch is heated to 120 ℃, controlling the shearing rate to 1200rpm, adding a composite additive, continuously heating to 150-165 ℃ and mixing at a high speed for 15-22min, discharging the mixture into a cold mixing pot, reducing the temperature to 90 ℃, and extruding the mixture into a die by a double screw extruder to be cooled and molded to obtain the impact-resistant engineering plastic.
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