CN116836342B - Toughening agent, plastic material and outdoor display equipment - Google Patents

Toughening agent, plastic material and outdoor display equipment Download PDF

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Publication number
CN116836342B
CN116836342B CN202310928610.7A CN202310928610A CN116836342B CN 116836342 B CN116836342 B CN 116836342B CN 202310928610 A CN202310928610 A CN 202310928610A CN 116836342 B CN116836342 B CN 116836342B
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Prior art keywords
toughening agent
diisocyanate
parts
reaction
methacrylic acid
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CN116836342A (en
Inventor
王晓帆
张小峰
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Shanghai Goodview Electronic Technology Co ltd
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Shanghai Goodview Electronic Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/2845—Monohydroxy epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Abstract

The invention relates to the field of high polymer materials, in particular to a toughening agent, a plastic material and outdoor display equipment, wherein the toughening agent is obtained by copolymerizing methacrylic acid modified epoxy polyurethane, styrene, vinyl siloxane and methyl methacrylate.

Description

Toughening agent, plastic material and outdoor display equipment
Technical Field
The invention relates to the field of high polymer materials, in particular to a toughening agent, a plastic material and outdoor display equipment.
Background
At present, many outdoor display devices are arranged on commercial streets and used for rolling and playing advertisements or consultation, so that the information transmission effect can be effectively achieved, the grade of commercial streets is improved, the shells of the outdoor display devices are made of PVC materials, and the outdoor display devices are installed outdoors in a severe working environment, so that the PVC shells are required to have a good protection effect on electronic devices inside the shells.
PVC is a high polymer formed by polymerizing vinyl chloride monomers through free radicals, and defects such as chloromethyl structure, allyl chloride structure, tertiary chloride structure and the like are caused in PVC by chain transfer reaction and double-radical coupling termination reaction in the polymerization process. The existence of the defects reduces the performance of the PVC material, and a large number of polar bonds C-Cl bonds in the PVC molecular chain cause larger acting force between molecules, so that the material is hard and brittle. The pure PVC material has poor toughness at room temperature and low temperature and is easy to crack when being impacted by external force, which limits the application of the PVC material, and the addition of the toughening agent can improve the impact strength of the PVC material, but also can reduce the tensile strength and the bending strength.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides a toughening agent, a plastic material and outdoor display equipment.
The technical scheme adopted is as follows:
a toughening agent is prepared from methacrylic acid modified epoxy polyurethane, styrene, vinyl siloxane and methyl methacrylate through copolymerizing.
Further, the preparation method of the methacrylic acid modified epoxy-terminated polyurethane comprises the following steps:
under the protection of nitrogen, uniformly mixing polyethylene glycol and diisocyanate, heating to 70-80 ℃ for reaction for 1-3 hours, cooling to 45-55 ℃, adding epoxy propanol, heating to 60-70 ℃ for reaction for 3-5 hours after heat preservation and stirring for 30-60 minutes, obtaining epoxy-terminated polyurethane, heating the epoxy-terminated polyurethane to 80-100 ℃, adding tetrabutylammonium bromide and methacrylic acid, stirring for heat preservation and reaction for 3-5 hours, and then recovering the room temperature.
Further, the diisocyanate is any one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
Further, the molar ratio of the polyethylene glycol, the diisocyanate and the epoxypropanol is 1:2 to 2.2:2 to 2.05.
Further, the molar ratio of the epoxy-terminated polyurethane to the methacrylic acid is 1:1 to 1.2.
Further, the preparation method of the toughening agent comprises the following steps:
adding the methacrylic acid modified epoxy polyurethane, styrene, vinyl siloxane and methyl methacrylate into dimethylbenzene, uniformly mixing, adding a free radical initiator and trimethylolpropane, uniformly mixing, degassing, heating a reaction system to 40-60 ℃ for reaction for 1-2 h, heating to 70-80 ℃ for reaction for 3-6 h, heating to 100-110 ℃ for reaction for 1-2 h, distilling under reduced pressure to remove dimethylbenzene, and finally drying, cooling and crushing.
The invention also provides a plastic material comprising the toughening agent.
Further, the plastic material comprises the following components in parts by weight:
80 to 100 parts of PVC resin, 40 to 60 parts of ABS resin, 0.5 to 1 part of calcium stearate, 0.5 to 1 part of paraffin, 40 to 60 parts of light calcium carbonate, 0.1 to 0.5 part of antioxidant 1141, 0.1 to 0.5 part of antioxidant 1076, 0.1 to 0.5 part of ultraviolet absorbent UV to 531, 0.1 to 0.5 part of lanthanum acetylacetonate and 5 to 10 parts of toughening agent according to any one of claims 1 to 6.
The invention also provides an outdoor display device which comprises the plastic material.
The invention has the beneficial effects that:
the invention provides a toughening agent, methacrylic acid modified epoxy polyurethane is used as a large monomer for copolymerization, the obtained copolymer is used as the toughening agent, the impact strength of plastics can be effectively improved at low content, the introduction of vinyl siloxane can further improve the toughening and reinforcing effects, the toughening agent is distributed in a plastic matrix, and under the action of external impact force, a large number of silver marks and shearing bands are deformed and developed, and a large amount of energy can be absorbed, so that the impact strength of plastics can be obviously improved.
Drawings
FIG. 1 is a cross-sectional SEM image of a plastic material prepared according to example 1 of the present invention.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The technology not mentioned in the present invention refers to the prior art, and unless otherwise indicated, the following examples and comparative examples are parallel tests, employing the same processing steps and parameters.
PVC resin: s-1000, brand Qi Lu petrifaction;
ABS resin: model LA-8Q, available from shandong leon new materials technologies inc;
calcium stearate: purchased from Shijia Chenjian mineral products Co., ltd;
paraffin wax: purchased from wegian building materials limited;
light calcium carbonate: purchased from Shijia Chenjian mineral products Co., ltd;
antioxidant 1141: IRGANOX 1141, brand basf;
antioxidant 1076: purchased from Shandong national chemical Co., ltd;
ultraviolet absorber UV-531: purchased from Shandong national chemical Co., ltd;
lanthanum acetylacetonate: purchased from Shandong Xu Chemie Co., ltd;
toughening agent: and (5) self-making.
Example 1:
a plastic material comprising, in parts by weight:
90 parts of PVC resin, 50 parts of ABS resin, 0.8 part of calcium stearate, 0.5 part of paraffin, 50 parts of light calcium carbonate, 0.3 part of antioxidant 1141, 0.5 part of antioxidant 1076, 0.5 part of ultraviolet absorber UV-531, 0.25 part of lanthanum acetylacetonate and 6 parts of toughening agent.
The toughening agent is prepared by copolymerizing methacrylic acid modified epoxy polyurethane, styrene, vinyl siloxane and methyl methacrylate, and the specific preparation method is as follows:
under the protection of nitrogen, uniformly mixing polyethylene glycol 2000 with hexamethylene diisocyanate, heating to 70 ℃ for reaction for 2 hours, closing heating, naturally cooling to 50 ℃, adding epoxypropanol, wherein the molar ratio of the polyethylene glycol 2000 to the diisocyanate to the epoxypropanol is 1:2.1:2.05, at the temperature, heating to 70 ℃ for reaction for 5 hours after heat preservation and stirring for 60min, so as to obtain epoxy-terminated polyurethane, heating the epoxy-terminated polyurethane to 100 ℃, adding tetrabutylammonium bromide and methacrylic acid, wherein the molar ratio of the epoxy-terminated polyurethane to the methacrylic acid to the tetrabutylammonium bromide is 1:1.2:0.02, carrying out heat preservation reaction for 5 hours under stirring, recovering room temperature to obtain methacrylic acid modified epoxy polyurethane, adding 12 parts by weight of methacrylic acid modified epoxy polyurethane, 10 parts by weight of styrene, 5 parts by weight of vinyltriethoxysilane and 53 parts by weight of methyl methacrylate into 300 parts by weight of dimethylbenzene, uniformly mixing, adding 0.8 part by weight of AIBN and 10 parts by weight of trimethylolpropane, uniformly mixing, degassing for 15 minutes, heating a reaction system to 60 ℃ for reaction for 2 hours, heating to 80 ℃ for reaction for 5 hours, heating to 110 ℃ for reaction for 2 hours, carrying out reduced pressure distillation to remove the dimethylbenzene, finally drying at 80 ℃ for 24 hours, cooling for 24 hours, and crushing to 400 meshes.
The preparation method of the plastic material comprises the following steps:
the raw materials are weighed after drying, pre-mixed in a high speed mixer at a rotational speed of about 2000-3000 r/min, the pre-mixture is fed into a twin screw extruder, pellets are prepared by melt extrusion, the screw speed is maintained at about 300r/min and the torque value is maintained at about 50-60% using a temperature of about 140-160 ℃, and the operation is performed under standard processing conditions well known to those skilled in the art, after blending, extrusion, cooling, pelleting, and after extrusion of the pellets, drying at 80 ℃ for 24 hours before molding the test specimen. The molding process is performed with a temperature range of 165-175 c and a mold temperature maintained at about 60 c.
Example 2:
a plastic material comprising, in parts by weight:
100 parts of PVC resin, 60 parts of ABS resin, 1 part of calcium stearate, 1 part of paraffin, 60 parts of light calcium carbonate, 0.5 part of antioxidant 1141, 0.5 part of antioxidant 1076, 0.5 part of ultraviolet absorber UV-531, 0.5 part of lanthanum acetylacetonate and 10 parts of toughening agent.
Wherein the toughening agent is prepared by copolymerizing methacrylic acid modified epoxy polyurethane, styrene, vinyl triethoxysilane and methyl methacrylate, and the specific preparation method is the same as in example 1;
the preparation method of the plastic material is the same as in example 1.
Example 3:
a plastic material comprising, in parts by weight:
80 parts of PVC resin, 40 parts of ABS resin, 0.5 part of calcium stearate, 0.5 part of paraffin, 40 parts of light calcium carbonate, 0.1 part of antioxidant 1141, 0.1 part of antioxidant 1076, 0.1 part of ultraviolet absorbent UV-531, 0.1 part of lanthanum acetylacetonate and 5 parts of toughening agent.
Wherein the toughening agent is prepared by copolymerizing methacrylic acid modified epoxy polyurethane, styrene, vinyl triethoxysilane and methyl methacrylate, and the specific preparation method is the same as in example 1;
the preparation method of the plastic material is the same as in example 1.
Example 4:
a plastic material comprising, in parts by weight:
100 parts of PVC resin, 40 parts of ABS resin, 0.5 part of calcium stearate, 1 part of paraffin, 40 parts of light calcium carbonate, 0.5 part of antioxidant 1141, 0.1 part of antioxidant 1076, 0.5 part of ultraviolet absorber UV-531, 0.1 part of lanthanum acetylacetonate and 10 parts of toughening agent.
Wherein the toughening agent is prepared by copolymerizing methacrylic acid modified epoxy polyurethane, styrene, vinyl triethoxysilane and methyl methacrylate, and the specific preparation method is the same as in example 1;
the preparation method of the plastic material is the same as in example 1.
Example 5:
a plastic material comprising, in parts by weight:
80 parts of PVC resin, 60 parts of ABS resin, 1 part of calcium stearate, 0.5 part of paraffin, 60 parts of light calcium carbonate, 0.1 part of antioxidant 1141, 0.5 part of antioxidant 1076, 0.1 part of ultraviolet absorber UV-531, 0.5 part of lanthanum acetylacetonate and 5 parts of toughening agent.
Wherein the toughening agent is prepared by copolymerizing methacrylic acid modified epoxy polyurethane, styrene, vinyl triethoxysilane and methyl methacrylate, and the specific preparation method is the same as in example 1;
the preparation method of the plastic material is the same as in example 1.
Comparative example 1:
substantially the same as in example 1, except that commercially available Japanese Brillouin MBS B-513 was used instead of the homemade toughening agent.
Comparative example 2:
substantially the same as in example 1, except that the homemade toughening agent was replaced with a commercially available Mitsubishi ACR P-551A toughening agent.
Comparative example 3:
substantially the same as in example 1, except that commercially available chlorinated polyethylene CPE-135A was used in place of the homemade toughening agent.
Comparative example 4:
substantially the same as in example 1, except that vinyltriethoxysilane was not added in the preparation of the toughening agent.
Performance test:
the plastic materials prepared in examples 1 to 5 and comparative examples 1 to 4 of the present invention were used as test samples for performance test;
the stretching performance is measured according to GB/T1040-2006 "measurement of Plastic stretching Property", and the stretching speed is 20mm/min;
bending performance is measured according to GB/T9341-2008 "measurement of Plastic bending Property", and bending speed is 5mm/min;
impact Strength according to GB/T1043.1-2008 section 1 of impact Property of Plastic simply supported Beam: the notch type is A type as measured in non-instrumented impact test;
the test results are shown in table 1 below:
table 1:
as can be seen from the above Table 1, the plastic material prepared by the present invention has excellent mechanical properties, and the addition of the self-made toughening agent can greatly improve the impact strength of the plastic material by comparing with comparative examples 1 to 3.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. The toughening agent is characterized by being obtained by copolymerizing methacrylic acid modified epoxy-terminated polyurethane with styrene, vinyl siloxane and methyl methacrylate;
the weight ratio of the methacrylic acid modified epoxy polyurethane to styrene, vinyl siloxane and methyl methacrylate is 12:10:5:53;
the preparation method of the methacrylic acid modified epoxy-terminated polyurethane comprises the following steps:
under the protection of nitrogen, uniformly mixing polyethylene glycol and diisocyanate, heating to 70-80 ℃ for reaction for 1-3 hours, cooling to 45-55 ℃, adding epoxy propanol, heating to 60-70 ℃ for reaction for 3-5 hours after heat preservation and stirring for 30-60 minutes, obtaining epoxy-terminated polyurethane, heating the epoxy-terminated polyurethane to 80-100 ℃, adding tetrabutylammonium bromide and methacrylic acid, and recovering room temperature after heat preservation and reaction for 3-5 hours under stirring;
the preparation method of the toughening agent comprises the following steps:
adding the methacrylic acid modified epoxy polyurethane, styrene, vinyl siloxane and methyl methacrylate into dimethylbenzene, uniformly mixing, adding a free radical initiator and trimethylolpropane, uniformly mixing, degassing, heating a reaction system to 40-60 ℃ for reaction for 1-2 h, heating to 70-80 ℃ for reaction for 3-6 h, heating to 100-110 ℃ for reaction for 1-2 h, distilling under reduced pressure to remove dimethylbenzene, and finally drying, cooling and crushing.
2. The toughening agent according to claim 1, wherein the diisocyanate is any one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate.
3. The toughening agent according to claim 1, wherein the molar ratio of polyethylene glycol, diisocyanate, epoxypropanol is 1:2 to 2.2:2 to 2.05.
4. The toughening agent according to claim 1, wherein the molar ratio of the epoxy-terminated polyurethane to methacrylic acid is 1:1 to 1.2.
5. A plastics material comprising a toughening agent according to any one of claims 1 to 4.
6. The plastic material of claim 5, comprising, in parts by weight:
80 to 100 parts of PVC resin, 40 to 60 parts of ABS resin, 0.5 to 1 part of calcium stearate, 0.5 to 1 part of paraffin, 40 to 60 parts of light calcium carbonate, 0.1 to 0.5 part of antioxidant 1141, 0.1 to 0.5 part of antioxidant 1076, 0.1 to 0.5 part of ultraviolet absorbent UV-531, 0.1 to 0.5 part of lanthanum acetylacetonate and 5 to 10 parts of toughening agent according to any one of claims 1 to 4.
7. An outdoor display device comprising the plastic material of claim 6.
CN202310928610.7A 2023-07-27 2023-07-27 Toughening agent, plastic material and outdoor display equipment Active CN116836342B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1312835A (en) * 1998-07-14 2001-09-12 三菱丽阳株式会社 Impact modifier, process for production, and resin composition containing same
KR20090038271A (en) * 2007-10-15 2009-04-20 주식회사 티앤엘 Polyurethane-acrylate hybrid resin contained plastisol compound
CN112759864A (en) * 2020-12-30 2021-05-07 金发科技股份有限公司 PVC/ABS alloy material and preparation method and application thereof
CN112795113A (en) * 2020-12-30 2021-05-14 金发科技股份有限公司 PVC alloy material and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1312835A (en) * 1998-07-14 2001-09-12 三菱丽阳株式会社 Impact modifier, process for production, and resin composition containing same
KR20090038271A (en) * 2007-10-15 2009-04-20 주식회사 티앤엘 Polyurethane-acrylate hybrid resin contained plastisol compound
CN112759864A (en) * 2020-12-30 2021-05-07 金发科技股份有限公司 PVC/ABS alloy material and preparation method and application thereof
CN112795113A (en) * 2020-12-30 2021-05-14 金发科技股份有限公司 PVC alloy material and preparation method and application thereof

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