CN110903529A - Low-odor low-VOC thermoplastic plastic - Google Patents
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention discloses a low-odor low-VOC thermoplastic plastic which comprises, by weight, 40-90 parts of a high polymer base material, 1-50 parts of an inorganic filler and 0-20 parts of an additive, wherein the inorganic filler comprises attapulgite. According to the invention, the porous mineral substance attapulgite is selected as the inorganic filler, the pore canal and pores of the attapulgite penetrate through the inside of the whole crystal structure, the attapulgite has the function of a molecular sieve, and the attapulgite has a large specific surface area and very strong adsorption performance.
Description
Technical Field
The invention belongs to the field of automotive interior materials, and particularly relates to a low-odor low-VOC thermoplastic plastic.
Background
Thermoplastic plastics are widely applied in the automobile industry due to the characteristics of high cost performance, low density, excellent heat resistance, chemical corrosion resistance, easy forming and processing, easy recycling and the like. However, the main chain of the thermoplastic matrix is degraded by light, heat, mechanical external force, oxidation reaction, etc., and generates substances such as alkane, aldehyde ketone, etc. through radical reaction, which results in an increase in the content of Volatile Organic Compounds (VOC) in the polymer matrix composite. The reasons of air pollution in automobiles are various, and since VOC release can cause a certain degree of harm to human health, people feel dizzy, nausea and inattention in such an environment for a short time, and breathe for a long time in such an environment, the air pollution in automobiles is easy to cause permanent damage to the nervous system and body organs of people, and even more, the air pollution causes cancer.
Disclosure of Invention
The invention aims to provide a low-odor low-VOC thermoplastic plastic, which has the innovation point that the porous mineral substance attapulgite is selected as an inorganic filler, the framework structure of the thermoplastic plastic is three-dimensional, zeolite pore channels and pores penetrate through the whole crystal structure, the thermoplastic plastic is a porous mineral substance and has the function of a molecular sieve, and the attapulgite has large specific surface area and strong adsorption performance. The attapulgite not only plays a certain reinforcing role to the matrix, but also can effectively utilize the porous property of the attapulgite to adsorb VOC, thereby solving the problem that the VOC release of the automotive interior material is harmful to the health of people.
In order to achieve the purpose, the technical scheme of the invention is as follows: the low-odor low-VOC thermoplastic plastic comprises, by weight, 40-90 parts of a high polymer base material, 1-50 parts of an inorganic filler and 0-20 parts of an additive, wherein the inorganic filler comprises attapulgite. The attapulgite has a special three-dimensional structure and a unique fiber needle shape; the high-purity and high-dispersion attapulgite needle-like fiber has a length of 1 μm and a width of 0.01. mu.m. The crystal structure of the attapulgite consists of most basic rod-shaped single crystals, crystal bundles formed by single crystal agglomeration and aggregates formed by crystal bundle agglomeration; compared with common inorganic mineral powder, the attapulgite has larger specific surface area, stronger adsorption capacity, stable rheological property and heat resistance, and more stable adsorption and desorption properties than common inorganic minerals, and can still maintain good stability at high temperature and in saline water.
Further, the inorganic filler is composed of one or more of bentonite, kaolin, activated carbon and calcium carbonate and attapulgite.
Further, the weight of the attapulgite is 0.01-100% of the weight of the inorganic filler.
Further, the polymer substrate is composed of one or more of PE, PP, PET, PA6, PBT, PU, PVC, PS, PC, ABS and TPO.
Further, the additive comprises, by weight, 0-10 parts of a plasticizer, 0-5 parts of an antioxidant, 0-3 parts of a light stabilizer and 0-3 parts of an ultraviolet absorber.
Further, the plasticizer is composed of one or more of dibutyl phthalate, dihexyl phthalate, epoxy butyl stearate, dioctyl adipate and trichloroethyl phosphate.
Further, the antioxidant is composed of one or more of an antioxidant 1010, an antioxidant 168, an antioxidant 1076, and an antioxidant 1098.
Further, the light stabilizer consists of one or more of the light stabilizer HTP or the light stabilizer 744.
Further, the ultraviolet absorbent is composed of one or more of UV-326, UV327 and UV 328.
Further, the attapulgite is modified attapulgite.
The modification method of the modified attapulgite comprises the following steps:
a. acidifying: under the condition of room temperature, the weight portions are as follows: adding 50 ml-200 ml of H into 1-100 parts of attapulgite and 0.1-10 parts of sodium hexametaphosphate2O, mixing, magnetically stirring for 20-60 min, and performing ultrasonic treatment for 30-60 min; heating and stirring the mixed solution for 20-40 min under the water bath condition of 50-80 ℃, standing for 1-4 h after the reaction is finished, removing impurities at the bottom of the container, repeatedly washing the suspension to be neutral, and performing centrifugal drying to obtain acidized attapulgite;
b. drying the acidified attapulgite for 6-12H at 60-90 ℃, taking 1-100 parts by weight of acidified attapulgite, and pouring 10-500 mL of ethanol and 10-100 mL of H2In a container of O, ultrasonically stirring for 30-60 min to uniformly disperse the acidified attapulgite in the liquid, dripping an organic modifier at 50-70 ℃ for reflux stirring, and adjusting the pH to 3-4 by adopting glacial acetic acid, citric acid or carbonic acid; and cooling to room temperature after the reaction is finished, repeatedly washing, centrifuging, drying in an oven at the temperature of 60-80 ℃, finally vacuumizing the oven, heating to 120 ℃, and drying for 12 hours to obtain the product, namely the organically modified attapulgite.
Before organic modification, attapulgite is agglomerated and accumulated, the impurities in the pore canal are more, so that the adjustment and control of gas cannot be realized, the impurities in the pore diameter of the attapulgite are removed through acidification treatment and organic modification, the pore canal in the pore canal is dredged, and the adjustment of carbon dioxide in the system is realized; more hydroxyl groups can be exposed from the modified attapulgite, so that the organic modifier can better react with the hydroxyl groups on the surface of the attapulgite so as to be attached to the surface of the attapulgite, the hydrophilic-lipophilic conversion of the surface of the attapulgite is realized, the surface of the attapulgite is converted into lipophilic functional groups, and the carbon dioxide can be more effectively regulated and the ethylene can be more effectively adsorbed by reacting with the ethylene; the attapulgite after organic modification can be dispersed in the polymer more uniformly and has better compatibility with the polymer, so that the attapulgite can also play a role in enhancing the toughness of the polymer.
The invention has the beneficial effects that: according to the invention, the porous mineral substance attapulgite is selected as the inorganic filler, the pore canal and pores of the attapulgite penetrate through the inside of the whole crystal structure, the attapulgite has the function of a molecular sieve, and the attapulgite has a large specific surface area and very strong adsorption performance. The attapulgite not only plays a certain reinforcing role to the matrix, but also can effectively utilize the porous property of the attapulgite to adsorb VOC, thereby solving the problem that the VOC release of the automotive interior material is harmful to the health of people.
Drawings
FIG. 1 shows the reaction formula of the present invention for modifying the surface of attapulgite.
FIG. 2 shows the effect of the addition of attapulgite on the VOCs detection results.
FIG. 3 is a graph showing the effect of attapulgite addition on thermoplastic tensile strength.
FIG. 4 is a graph showing the effect of attapulgite addition on the flexural strength of thermoplastics.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.
Example 1: the low-odor low-VOC thermoplastic plastic comprises the following components, by weight, 40 parts of a high polymer base material and 1 part of an inorganic filler, wherein the inorganic filler comprises attapulgite; the polymer base material is composed of one or more of PE, PP, PET, PA6, PBT, PU, PVC, PS, PC, ABS and TPO; the inorganic filler is composed of one or more of bentonite, kaolin, active carbon and calcium carbonate and attapulgite, and the weight of the attapulgite is 0.01 percent of the weight of the inorganic filler.
Example 2: the low-odor low-VOC thermoplastic plastic comprises the following components, by weight, 65 parts of a high polymer base material, 25 parts of an inorganic filler and 10 parts of an additive, wherein the inorganic filler comprises attapulgite; the polymer base material consists of PE, PP and PET; the inorganic filler consists of bentonite, kaolin and attapulgite, and the weight of the attapulgite is 50 percent of that of the inorganic filler; the attapulgite is modified attapulgite; the additive comprises the following components, by weight, 5 parts of plasticizer, 3 parts of antioxidant, 2 parts of light stabilizer and 2 parts of ultraviolet absorbent; the plasticizer is composed of one or more of dibutyl phthalate, dihexyl phthalate, epoxy butyl stearate, dioctyl adipate and trichloroethyl phosphate; the antioxidant comprises one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant 1098; the light stabilizer consists of one or more of light stabilizer HTP and light stabilizer 744; the ultraviolet absorbent is composed of one or more of UV-326, UV327 and UV 328.
The modification method of the modified attapulgite comprises the following steps:
a. acidifying: under the condition of room temperature, the weight portions are as follows: adding 1 part of attapulgite and 0.1 part of sodium hexametaphosphate into 50ml of H2O, mixing, magnetically stirring for 20min, and performing ultrasonic treatment for 30 min; heating and stirring the mixed solution in a water bath at 50 ℃ for 20min, standing for 1h after the reaction is finished, removing impurities at the bottom of the container, repeatedly washing the suspension to be neutral, and performing centrifugal drying to obtain acidized attapulgite;
b. drying acidified attapulgite for 6H at 60 ℃, pouring 1 part by weight of acidified attapulgite into a container filled with 10mL of ethanol and 10mL of H2O, ultrasonically stirring for 30min to uniformly disperse the acidified attapulgite in liquid, dripping an organic modifier at 50 ℃, refluxing and stirring, and adjusting the pH to 3 by adopting glacial acetic acid or citric acid or carbonic acid; and cooling to room temperature after the reaction is finished, repeatedly washing, centrifuging, drying in a 60 ℃ oven, finally vacuumizing the drying oven, heating to 120 ℃, and drying for 12 hours to obtain the product, namely the organically modified attapulgite.
Example 3: the low-odor low-VOC thermoplastic plastic comprises the following components, by weight, 90 parts of a high polymer base material, 50 parts of an inorganic filler and 20 parts of an additive, wherein the inorganic filler comprises attapulgite; the polymer base material consists of PA6, PBT, PU and PVC; the inorganic filler consists of activated carbon, calcium carbonate and attapulgite, and the weight of the attapulgite is 80 percent of that of the inorganic filler; the attapulgite is modified attapulgite; the additive comprises the following components in parts by weight, 10 parts of plasticizer, 5 parts of antioxidant, 3 parts of light stabilizer and 3 parts of ultraviolet absorbent; the plasticizer consists of dibutyl phthalate and dihexyl phthalate; the antioxidant consists of an antioxidant 1010 and an antioxidant 168; the light stabilizer is light stabilizer HTP; the ultraviolet absorbent consists of UV-326 and UV 327.
The modification method of the modified attapulgite comprises the following steps:
a. acidifying: under the condition of room temperature, the weight portions are as follows: adding 50 parts of attapulgite and 0.15 part of sodium hexametaphosphate into 100ml of H2O, mixing, magnetically stirring for 40min, and performing ultrasonic treatment for 45 min; heating and stirring the mixed solution in a water bath at 65 ℃ for 30min, standing for 3h after the reaction is finished, removing impurities at the bottom of the container, repeatedly washing the suspension to be neutral, and performing centrifugal drying to obtain acidized attapulgite;
b. drying acidified attapulgite for 10H at 85 ℃, pouring 50 parts by weight of acidified attapulgite into a container filled with 250mL of ethanol and 55mL of H2O, ultrasonically stirring for 45min to uniformly disperse the acidified attapulgite in liquid, dripping an organic modifier at 60 ℃, refluxing and stirring, and adjusting the pH to 3.5 by adopting glacial acetic acid or citric acid or carbonic acid; and cooling to room temperature after the reaction is finished, repeatedly washing, centrifuging, drying in an oven at 70 ℃, finally vacuumizing the drying oven, heating to 120 ℃, and drying for 12 hours to obtain the product, namely the organically modified attapulgite.
Example 4: the low-odor low-VOC thermoplastic plastic comprises the following components, by weight, 80 parts of a high polymer base material, 30 parts of an inorganic filler and 15 parts of an additive, wherein the inorganic filler is attapulgite, and the attapulgite is modified attapulgite; the polymer substrate is composed of PS, PC, ABS and TPO; the additive comprises the following components, by weight, 8 parts of plasticizer, 2 parts of antioxidant, 1 part of light stabilizer and 1 part of ultraviolet absorbent; the plasticizer consists of epoxy butyl stearate, dioctyl adipate and trichloroethyl phosphate; the antioxidant consists of an antioxidant 1076 and an antioxidant 1098; the light stabilizer is light stabilizer 744; the ultraviolet absorbent consists of UV327 and UV 328.
The modification method of the modified attapulgite comprises the following steps:
a. acidifying: under the condition of room temperature, the weight portions are as follows: adding 100 parts of attapulgite and 0.110 part of sodium hexametaphosphate into 200ml of H2O, mixing, magnetically stirring for 60min, and performing ultrasonic treatment for 60 min; heating and stirring the mixed solution in a water bath at 80 ℃ for 40min, standing for 4h after the reaction is finished, removing impurities at the bottom of the container, repeatedly washing the suspension to be neutral, and performing centrifugal drying to obtain acidized attapulgite;
b. drying acidified attapulgite for 12H at 90 ℃, pouring 100 parts by weight of acidified attapulgite into a container filled with 500mL of ethanol and 100mL of H2O, ultrasonically stirring for 60min to uniformly disperse the acidified attapulgite in liquid, dripping an organic modifier at 70 ℃, refluxing and stirring, and adjusting the pH to 4 by adopting glacial acetic acid or citric acid or carbonic acid; and cooling to room temperature after the reaction is finished, repeatedly washing, centrifuging, drying in an oven at 80 ℃, finally vacuumizing the drying oven, heating to 120 ℃, and drying for 12 hours to obtain the product, namely the organically modified attapulgite.
The described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. The low-odor low-VOC thermoplastic plastic is characterized by comprising, by weight, 40-90 parts of a high polymer base material, 1-50 parts of an inorganic filler and 0-20 parts of an additive, wherein the inorganic filler comprises attapulgite.
2. The low odor, low VOC thermoplastic of claim 1 wherein said inorganic filler is comprised of one or more of bentonite, kaolin, activated carbon, calcium carbonate and attapulgite.
3. The low odor, low VOC thermoplastic of claim 2 wherein the attapulgite clay is present in an amount of 0.01% to 100% by weight of the inorganic filler.
4. The low odor, low VOC thermoplastic of claim 1, wherein said polymeric substrate is comprised of one or more of PE, PP, PET, PA6, PBT, PU, PVC, PS, PC, ABS, TPO.
5. The low odor and low VOC thermoplastic as claimed in claim 1, wherein said additive comprises the following components, by weight, 0-10 parts of plasticizer, 0-5 parts of antioxidant, 0-3 parts of light stabilizer, and 0-3 parts of ultraviolet absorber.
6. The low odor, low VOC thermoplastic of claim 5 wherein said plasticizer is comprised of one or more of dibutyl phthalate, dihexyl phthalate, butyl epoxystearate, dioctyl adipate, and trichloroethyl phosphate.
7. The low odor, low VOC thermoplastic of claim 5 wherein said antioxidant is comprised of one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 1098.
8. The low odor, low VOC thermoplastic of claim 5 wherein said light stabilizer is comprised of one or more of the light stabilizer HTP, light stabilizer 744.
9. The low odor, low VOC thermoplastic of claim 5 wherein said ultraviolet absorber is comprised of one or more of UV-326, UV327, UV 328.
10. The low odor, low VOC thermoplastic of claim 3 wherein said attapulgite is a modified attapulgite.
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Cited By (2)
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CN112757736A (en) * | 2021-01-22 | 2021-05-07 | 王聪 | TPO waterproof coiled material and preparation method thereof |
CN115246981A (en) * | 2022-08-22 | 2022-10-28 | 山东海科创新研究院有限公司 | Low-VOC high-performance ABS composite material and preparation method thereof |
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CN101759950A (en) * | 2008-12-23 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Novel low-odor and low-emission ABS resin compound and preparation method thereof |
CN101760010A (en) * | 2008-12-26 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Low odor and distribute nylon 6 combination and preparation method thereof |
CN106566235A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature-resistant nylon/attapulgite composite material and preparation method thereof |
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2019
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CN101469094A (en) * | 2007-12-28 | 2009-07-01 | 上海普利特复合材料股份有限公司 | Novel low odor polypropylene composite material and preparation thereof |
CN101759950A (en) * | 2008-12-23 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Novel low-odor and low-emission ABS resin compound and preparation method thereof |
CN101760010A (en) * | 2008-12-26 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Low odor and distribute nylon 6 combination and preparation method thereof |
CN106566235A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature-resistant nylon/attapulgite composite material and preparation method thereof |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112757736A (en) * | 2021-01-22 | 2021-05-07 | 王聪 | TPO waterproof coiled material and preparation method thereof |
CN115246981A (en) * | 2022-08-22 | 2022-10-28 | 山东海科创新研究院有限公司 | Low-VOC high-performance ABS composite material and preparation method thereof |
CN115246981B (en) * | 2022-08-22 | 2023-10-24 | 山东海科创新研究院有限公司 | Low-VOC (volatile organic compound) high-performance ABS (Acrylonitrile butadiene styrene) composite material and preparation method thereof |
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