CN114479260B - Heat-resistant light diffusion polypropylene composition and application thereof, heat-resistant light diffusion polypropylene and preparation method and application thereof - Google Patents

Heat-resistant light diffusion polypropylene composition and application thereof, heat-resistant light diffusion polypropylene and preparation method and application thereof Download PDF

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CN114479260B
CN114479260B CN202011148010.1A CN202011148010A CN114479260B CN 114479260 B CN114479260 B CN 114479260B CN 202011148010 A CN202011148010 A CN 202011148010A CN 114479260 B CN114479260 B CN 114479260B
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polypropylene
heat
resistant light
phenylmaleimide
light diffusion
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CN114479260A (en
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茹越
郭照琰
赖金梅
胡晨曦
戚桂村
李秉海
王湘
张江茹
韩朋
宋志海
蒋海斌
蔡传伦
姜超
刘文璐
张红彬
张晓红
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

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Abstract

The invention relates to the field of high polymer materials, and discloses a heat-resistant photodiffusion polypropylene composition, heat-resistant photodiffusion polypropylene, and a preparation method and application thereof. The polypropylene composition comprises polypropylene, maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microspheres and silicone resin microspheres; the amount of the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere is 0.1 to 10 parts by weight and the amount of the organosilicon resin microsphere is 0.01 to 0.5 part by weight based on 100 parts by weight of polypropylene. The heat-resistant light diffusion polypropylene composition can improve the light diffusion performance of a polypropylene material and can improve the heat deformation temperature of the polypropylene composition, so that the heat-resistant light diffusion polypropylene prepared from the composition can meet the use requirement under the high-temperature condition.

Description

Heat-resistant light diffusion polypropylene composition and application thereof, heat-resistant light diffusion polypropylene and preparation method and application thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a heat-resistant light diffusion polypropylene composition and application thereof, and a preparation method and application thereof.
Background
The LED lamp has the advantages of high efficiency, long service life and the like, and is widely applied to the fields of indoor illumination, automobile illumination and the like. However, the light intensity of the LED lamp per unit area is too high, and symptoms such as dizziness, visual discomfort and the like can be generated after direct vision. Meanwhile, similar problems are encountered when LEDs and LCDs are used as display materials. Therefore, it is required to use a material that can transform a point light source into a surface light source due to diffusion of the material when light passes through the material, so that the light becomes gentle, and the material is called a light diffusion material. In the past, a large number of researchers have used transparent resins such as polycarbonate and polymethyl methacrylate as the matrix of light diffusion materials, but such resins are expensive and have a high density, which can affect their use in light-weight and low-cost lamps.
Therefore, the use of polypropylene as a matrix for preparing light diffusion materials is a current research hotspot, wherein CN109593275a discloses a light diffusion polypropylene material for LED lamp covers and a preparation method thereof; comprises the following components in parts by weight: 80-90 parts of polypropylene copolymer; 10-20 parts of homo-polypropylene; 0.3-0.8 part of inducer; 0.05-0.1 part of initiator; 1-3 parts of light dispersing agent; 0.6-1 part of antioxidant; 0.2-1 part of lubricant; wherein the initiator is dicumyl peroxide; the light dispersing agent is organic silicon light dispersing agent. During preparation, a zoned feeding system is adopted, and extrusion granulation is carried out in a double-screw extruder.
CN109422961a discloses a flame-retardant light diffusion polypropylene composite material for an LED and a product thereof, wherein the composite material comprises the following components in parts by weight: 100 parts of homopolymerized polypropylene, 2-5 parts of compound flame retardant, 1-5 parts of organic silicon light dispersing agent, 1-5 parts of barium sulfate light dispersing agent, 1-2 parts of light stabilizer and 2-3 parts of chemical modifier.
However, in the prior art, two different light diffusion polypropylene materials are adopted, and the polypropylene material with the light diffusion effect is prepared by adding the traditional organic silicon light diffusion agent and the inorganic salt light diffusion agent. However, the problem that the LED lamp generates large heat during operation is neglected in the research and production work, so that the polypropylene material used as the light diffusion material of the LED needs to be used under a high temperature condition, and the problem is not solved in the prior art.
Disclosure of Invention
The invention aims to solve the problems that the heat resistance and the heat deformation temperature of a flame-retardant light diffusion polypropylene material for an LED are low and the long-term use of the LED cannot be met in the prior art, and provides a heat-resistant light diffusion polypropylene composition and application, a heat-resistant light diffusion polypropylene and a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a heat-resistant light diffusion polypropylene composition, characterized in that the polypropylene composition comprises polypropylene, maleic anhydride/N-phenylmaleimide/α -methylstyrene copolymer microspheres and silicone resin microspheres;
the amount of the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere is 0.1 to 10 parts by weight and the amount of the organosilicon resin microsphere is 0.01 to 0.5 part by weight based on 100 parts by weight of polypropylene.
In a second aspect, the present invention provides a heat-resistant light-diffusing polypropylene, which is characterized in that the heat-resistant light-diffusing polypropylene is prepared from the heat-resistant light-diffusing polypropylene composition.
A third aspect of the present invention provides a method for preparing the above heat-resistant light diffusion polypropylene.
A fourth aspect of the present invention provides the use of the above heat-resistant light-diffusing polypropylene composition or heat-resistant light-diffusing polypropylene in an illumination body.
Through the technical scheme, the heat-resistant light diffusion polypropylene composition and application thereof, and the heat-resistant light diffusion polypropylene and the preparation method and application thereof provided by the invention have the following beneficial effects:
the heat-resistant light diffusion polypropylene composition adopts maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microspheres and organic silicon resin microspheres as light diffusion agents to improve the light diffusion performance of the polypropylene material. The composition obtained by the method can improve the light diffusion performance of the polypropylene material and the heat distortion temperature of the polypropylene composition, so that the service performance of the material under high temperature conditions is improved.
Furthermore, in the invention, the used maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere has photoluminescence effect, and can convert partial ultraviolet light into visible light, so that the light transmittance can be kept high under a large addition amount, and the microsphere can be used as a lighting body material under a high-temperature condition.
Furthermore, in the preparation method of the heat-resistant light diffusion polypropylene material, the general rubber-plastic blending equipment is used for blending all components for preparing the composition at one time to prepare the light diffusion polypropylene composition with heat resistance, and the preparation method is simple in process and easy to implement.
Drawings
FIG. 1 is an infrared spectrum of copolymer microspheres of preparation example 1;
FIG. 2 is a scanning electron microscope image of the copolymer microsphere of preparation example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a heat-resistant light diffusion polypropylene composition, which is characterized in that the polypropylene composition comprises polypropylene, maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microspheres and silicone resin microspheres;
the amount of the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere is 0.1 to 10 parts by weight and the amount of the organosilicon resin microsphere is 0.01 to 0.5 part by weight based on 100 parts by weight of polypropylene.
In the composition, the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere and the organic silicon resin microsphere together play a role of a light diffusion agent, and the light diffusion performance of polypropylene can be obviously improved by matching the particle size and the refractive index of the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere and the organic silicon resin microsphere. Further, the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere has high molecular chain rigidity and high glass transition temperature, can be uniformly dispersed in a polypropylene matrix, and can effectively improve the heat distortion temperature of the composition, so that the composition can meet the use requirement under the high-temperature condition.
In order to further improve the light diffusion property of the composition and improve the heat resistance of the composition, it is preferable that the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere is used in an amount of 0.3 to 10 parts by weight and the silicone resin microsphere is used in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of polypropylene.
Maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microspheres
In the invention, the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere has high molecular chain rigidity and high glass transition temperature, and can effectively improve the heat distortion temperature of the composition, thereby enabling the composition to meet the use requirement under the high-temperature condition. Compared with the conventional inorganic light dispersing agent and maleic anhydride binary copolymerization microsphere in the prior art, the maleic anhydride/N-phenyl maleimide/alpha-methyl styrene copolymer microsphere has excellent compatibility with matrix polypropylene, so that higher light transmittance can be maintained under larger addition amount.
According to the invention, in the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere, the molar content of the maleic anhydride structural unit is 30-52%, the molar content of the N-phenylmaleimide structural unit is 5-30% and the molar content of the alpha-methylstyrene structural unit is 20-45%, based on the total molar amount of each structural unit of the copolymer.
In the present invention, the sum of the molar contents of the maleic anhydride structural unit, the N-phenylmaleimide structural unit and the alpha-methylstyrene structural unit is 100%.
In the invention, the content of each structural unit in the copolymer is tested by adopting 1H NMR, and the testing method is obtained by calculating the proportion of the peak area corresponding to the characteristic hydrogen in the corresponding structural unit in the 1H NMR.
In the invention, the specific comonomer is copolymerized according to the dosage proportion defined by the invention, so that the obtained maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer has microspheres with good uniformity, the prepared copolymer microspheres have good dispersibility in a medium, aggregation among the microspheres is not easy to occur, and the copolymer microspheres are used as a light dispersing agent, so that the composition has a photoluminescence effect and the heat resistance of the composition can be obviously improved.
Further, in order to obtain a copolymer microsphere having more excellent properties, more uniform microsphere morphology, and further more excellent photoluminescence effect and heat resistance, it is preferable that the molar content of the maleic anhydride structural unit is 30 to 50%, the molar content of the N-phenylmaleimide structural unit is 5 to 25%, and the molar content of the α -methylstyrene structural unit is 20 to 40% based on the total molar amount of each structural unit of the copolymer.
According to the invention, the particle size of the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microspheres is 1500-2500nm, preferably 1500-2000nm.
In the invention, the particle size of the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere is measured by a scanning electron microscope.
In one embodiment of the invention, the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microspheres are prepared according to the following method:
(1) In inert atmosphere, dissolving a polymerization monomer and an initiator in a reaction medium to form a homogeneous solution;
(2) Carrying out polymerization reaction on the homogeneous solution to obtain copolymer emulsion suspension, and then carrying out centrifugal separation to obtain the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere;
the polymeric monomers include maleic anhydride, N-phenylmaleimide, and alpha-methylstyrene.
In the invention, a specific comonomer is copolymerized in a copolymerization mode, so that the prepared maleic anhydride/N-phenylmaleimide copolymer is microsphere with excellent uniformity, and the surface of the particle is clean, so that uniform microsphere particles and clean indication of copolymerization are prepared, the uniform microsphere particles can be well dispersed in a polypropylene matrix, and the effect of a light dispersing agent is realized.
According to the invention, the mass concentration of the polymerized monomer is 5 to 25% by weight, preferably 10 to 20% by weight, based on the total weight of the homogeneous solution.
According to the invention, the maleic anhydride is used in an amount of 30 to 50 wt.%, the N-phenylmaleimide is used in an amount of 20 to 50 wt.%, and the N-phenylmaleimide is used in an amount of 20 to 50 wt.%, based on the total weight of the polymerized monomers.
In the invention, in order to obtain the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere with uniform particles and excellent morphology, the inventor researches the respective dosage of maleic anhydride, N-phenylmaleimide and alpha-methylstyrene in the polymerization process, and the researches show that when each polymerization monomer meets the range, the prepared terpolymer microsphere has uniform particles and excellent particle morphology, and the particle surface is clean, and can be used as a modified polymer for a light dispersing agent, particularly for polypropylene, and the heat resistance temperature and photoluminescence performance of the polypropylene can be obviously improved.
Still further, the maleic anhydride is used in an amount of 39 to 45wt%, the N-phenylmaleimide is used in an amount of 25 to 42wt%, and the alpha-methylstyrene is used in an amount of 19 to 47wt%, based on the total weight of the polymerized monomers.
According to the invention, the initiator is an organic peroxide and/or an azo compound.
According to the present invention, the organic peroxide is at least one selected from dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
According to the invention, the azo compound is selected from azobisisobutyronitrile and/or azobisisoheptonitrile.
According to the invention, the mass concentration of the initiator is 0.1 to 4 wt.%, preferably 0.5 to 4 wt.%, more preferably 1 to 3 wt.%, based on the total weight of the homogeneous solution.
In the present invention, the total amount of maleic anhydride, N-phenylmaleimide, alpha-methylstyrene, initiator and reaction medium is 100% by weight.
According to the invention, the reaction medium is an alkyl ester of an organic acid.
In the invention, the organic acid alkyl ester is selected as a reaction medium, can be matched with the maleic anhydride, the N-phenyl maleimide and the alpha-methyl styrene with specific dosage, can realize the self-stabilization precipitation polymerization reaction of the maleic anhydride, the N-phenyl maleimide and the alpha-methyl styrene, does not need to add any stabilizer or auxiliary stabilizer in a polymerization reaction system, and has a self-stabilization dispersing effect.
According to the invention, the alkyl esters of organic acids have the formula R 1 COOR 2 Wherein R is 1 Selected from H, C 1-4 At least one of alkyl, phenyl and benzyl, R 2 Is C 1-10 Is a hydrocarbon group.
Preferably, R 1 Is C 1-4 R is alkyl and/or phenyl 2 Is C 1-7 Is a hydrocarbon group.
Still further, the reaction medium is selected from at least one of ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate.
According to the invention, the polymerization conditions include: the polymerization temperature is 60-90 ℃, preferably 60-80 ℃; the polymerization time is 3 to 24 hours, preferably 4 to 8 hours.
In the present invention, a water bath and/or an oil bath is used to provide the heat required for the polymerization of the present invention.
In the invention, a solid-liquid separation mode is adopted to separate the copolymer emulsion suspension obtained by the polymerization reaction so as to obtain the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere.
In the present invention, a solid-liquid separation method which is conventional in the prior art, preferably, a centrifugal separation method can be used.
In the invention, when centrifugal separation is adopted, the centrifugal rotating speed is 1000-3000rad/min, and the centrifugal time is 10-30min.
Organic silicon resin microsphere
In the invention, the organic silicon resin microsphere and the maleic anhydride/N-phenyl maleimide/alpha-methyl styrene copolymer microsphere are added into the composition to be matched with each other, so that the light diffusion performance of the composition can be improved, and the heat resistance deformation of the composition can be obviously improved, thereby obtaining the light diffusion polypropylene composition with heat resistance.
As the particle size of the silicone resin microspheres increases, the more pronounced it improves haze, but the greater the impact on light transmittance. In the present invention, it has been found through studies that when the particle diameter of the silicone resin microspheres is 0.1 to 100. Mu.m, preferably 1 to 50. Mu.m, more preferably 1.5 to 30. Mu.m, it is possible to improve the haze of the composition while not affecting the light transmittance of the composition, and achieve a balance between the haze and the light transmittance.
According to the invention, the silicone resin in the silicone resin microsphere is an organosiloxane.
Polypropylene
In the present invention, in order to allow light diffusing polypropylene to have both high light transmittance and high haze, a polypropylene copolymer having high light transmittance may be selected as a base material of the composition. Preferably, the polypropylene is a random copolymer polypropylene obtained by copolymerizing propylene and alpha-olefin.
In the present invention, the alpha-olefin is selected from ethylene and/or 1-butene.
According to the invention, the polypropylene has a melt index of 25-60/10min at 230℃and a load of 2.16 kg. When the melt index is too large or too small, the dispersion of the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microspheres and the silicone resin microspheres is affected, thereby affecting the light diffusion properties of the material. Further, when the melt index of polypropylene satisfies the above range, polypropylene has excellent processability.
Antioxidant
According to the invention, preferably, the composition further comprises an antioxidant. Preferably, the antioxidant is 0.1 to 0.5 parts by weight, preferably 0.2 to 0.5 parts by weight, based on 100 parts by weight of polypropylene.
In the present invention, the antioxidant may be at least one selected from the group consisting of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants. Specifically, the hindered phenol antioxidant may be a monophenol, a bisphenol, or a polyphenol; the phosphite antioxidant comprises alkyl phosphite and aryl phosphite; the sulfur ester antioxidant comprises a sulfur ester antioxidant, a thioether phenol antioxidant and a thiobisphenol antioxidant. The antioxidant can be a composite antioxidant, and can be a composite formed by mixing a plurality of hindered phenol antioxidants, phosphite antioxidants and sulfolipid antioxidants according to a certain mass ratio. The hindered phenol antioxidant, the phosphite antioxidant and the sulfolipid antioxidant are all known substances and are commercially available. Such as antioxidant 1010 (hindered phenol antioxidant), antioxidant 168 (phosphite antioxidant).
Other auxiliary agents
In the invention, other auxiliary agents can be also contained in the composition, so that the performance of polypropylene is not affected. The auxiliary agent may be at least one selected from the group consisting of a slipping agent, an antistatic agent, a lubricant, and a plasticizer.
In a second aspect, the present invention provides a heat-resistant light-diffusing polypropylene, which is characterized in that the heat-resistant light-diffusing polypropylene is prepared from the heat-resistant light-diffusing polypropylene composition.
According to the invention, the thermal deformation temperature of the light diffusion polypropylene is T2, and the thermal deformation temperature of the polypropylene is T1, wherein T2-T1 is more than or equal to 0.5 ℃; the light transmittance of the light diffusion polypropylene is more than 70%, and the haze is more than 80%.
According to the invention, T2-T1 is more than or equal to 1.5 ℃, the light transmittance of the light diffusion polypropylene is more than 70%, and the haze is more than 85%.
According to the invention, T2-T1 is more than or equal to 3 ℃, the light transmittance of the light diffusion polypropylene is more than 70%, and the haze is more than 90%.
In the invention, the transmittance and haze of the polypropylene are tested according to GB/T2410, and the thickness of a sample is 2mm.
A third aspect of the present invention provides a method for producing the above heat-resistant light diffusion polypropylene, characterized by comprising: the heat-resistant light diffusion polypropylene composition is prepared by evenly mixing and melt blending.
In one embodiment of the present invention, a heat resistant light diffusion polypropylene is prepared according to the following method: the components in the diffusion polypropylene composition are mixed according to the dosage, and the obtained mixture is extruded and granulated to obtain the light diffusion polypropylene. The extrusion temperature may be 185-215 ℃. Conventional extrusion pelletization can be carried out using an extruder conventional in the art, such as a twin screw extruder.
A fourth aspect of the present invention provides the use of the above heat resistant light diffusing polypropylene composition or the above heat resistant light diffusing polypropylene in a lighting body, preferably an LED lamp.
The present invention will be described in detail by examples. In the following examples of the present invention,
the polymerization yield (Cp) was calculated according to the following formula:
Cp＝Mp×100％/Mm
wherein Mp is the mass of the resulting polymer; mm is the total mass of the monomers added.
The morphology and the size of the copolymer microsphere are observed and measured by adopting a Scanning Electron Microscope (SEM);
the infrared spectrogram of the copolymer is tested by adopting FI-IR;
the content of each structural unit in the copolymer is adopted 1 H NMR was tested by 1 The content of each structural unit was measured by the ratio of the peak area corresponding to the characteristic hydrogen in the corresponding structural unit in H NMR.
The light transmittance and the haze are tested according to GB/T2410, and the thickness of a sample is 2mm;
heat distortion temperature was measured according to ISO-75 standard;
the comonomers maleic anhydride, N-phenylmaleimide and alpha-methylstyrene are all available from the technical Co.Ltd;
PP-1: the polypropylene M26ET is purchased from sea-compacting, the melt index is 25g/10min, and the heat distortion temperature is 81 ℃;
PP-2: the polypropylene M35ET is purchased from sea-compacting, the melt index is 36g/10min, and the heat distortion temperature is 76 ℃;
PP-3: the polypropylene M60ET is purchased from sea-compacting, the melt index is 60g/10min, and the heat distortion temperature is 108.2 ℃;
silicone resin microsphere B1: purchased from Dow Corning 30-424 (particle size 2-3 μm);
silicone resin microsphere B2: the purchase confidence KMP-590 (2-4 μm);
silicone resin microsphere B3: purchased from Kemaixin KM-9006 (particle size 6 μm).
Other reagents used in the examples and comparative examples are commercially available.
Preparation examples 1-6 were used to prepare maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microspheres.
Preparation example 1
10g of maleic anhydride, 0.8g of azodiisobutyronitrile, 5.9g of alpha-methylstyrene, 8.65g of N-phenylmaleimide and 87.8g of isoamyl acetate are added into a 500mL three-necked flask, after the materials are uniformly mixed, nitrogen is introduced for 20 minutes, the three-necked flask is moved into a water bath at 90 ℃ for reaction for 3 hours, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, and 117.89g of polymer microsphere A is obtained, and the corresponding polymer yield is 73.5%. The polymer microsphere size was 1500nm.
Subjecting the polymer microsphere A1 to 1 HNMR measurement, which measured that the molar content of maleic anhydride structural unit was 52% and that of N-phenylmaleimide structural unit was 29% based on the total molar amount of each structural unit in the polymerThe molar content of the ethylene structural unit was 19%, and the results are shown in Table 1.
FI-IR diagram of copolymer microsphere, 1785cm as shown in FIG. 1 -1 、1850cm -1 Is the characteristic absorption peak of anhydride group, 709cm -1 Is a special absorption peak of benzene ring, 1020-1300cm -1 Based on this, it was determined that the polymer was a maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer.
As can be seen from the SEM image of the copolymer microsphere shown in fig. 2, the particles of the copolymer microsphere are uniform, and the particle surface is clean and not contaminated.
Preparation example 2
14g maleic anhydride, 0.4g azodiisobutyronitrile, 11g alpha-methylstyrene, 6g N-phenylmaleimide and 120g butyl benzoate are added into a 500mL three-neck flask, after the materials are uniformly mixed, nitrogen is introduced for 20 minutes, the three-neck flask is moved into a water bath at 60 ℃ for reaction for 24 hours, and after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, so that 23.75g of polymer microsphere A is obtained, and the corresponding polymer yield is 76%. The polymer microsphere size was 2000nm.
Subjecting the polymer microsphere A2 to 1 HNMR measurement, which shows that the molar content of the maleic anhydride structural unit was 44%, the molar content of the N-phenylmaleimide structural unit was 18%, and the molar content of the α -methylstyrene structural unit was 38% based on the total molar amount of each structural unit in the polymer, is shown in table 1.
Preparation example 3
14g of maleic anhydride, 1.2g of azobisisobutyronitrile, 8g of alpha-methylstyrene, 8g of N-phenylmaleimide and 120g of isoamyl acetate are added into a 500mL three-neck flask, after the materials are uniformly mixed, nitrogen is introduced for 20 minutes, the three-neck flask is moved into a water bath at 70 ℃ for reaction for 5 hours, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at a rotating speed of 2000rad/min, and polymer microspheres A319.2g are obtained, and the corresponding polymer yield is 82.6%. The polymer microsphere size was 2400nm.
Subjecting the polymer microsphere A3 to 1 HNMR measurements were carried out to determine that the molar content of maleic anhydride structural units was 50%, the molar content of N-phenylmaleimide structural units was 29%, and the molar content of alpha-methylstyrene structural units was 21% based on the total molar amount of the structural units in the polymer, and the results are shown in Table 1.
Preparation example 4
6g of maleic anhydride, 0.89g of azodiisobutyronitrile, 10g of alpha-methylstyrene, 4g of N-phenylmaleimide and 82g of butyl butyrate are added into a 500mL three-neck flask, after the materials are uniformly mixed, nitrogen is introduced into the three-neck flask for 20 minutes, the three-neck flask is moved into a water bath with the temperature of 70 ℃ for reaction for 5 hours, and after the reaction is finished, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, so that polymer microspheres A419.85g are obtained, and the corresponding polymer yield is 87.4%. The polymer microsphere size was 2500nm.
Subjecting the polymer microsphere A4 to 1 HNMR measurement, which shows that the molar content of the maleic anhydride structural unit was 30%, the molar content of the N-phenylmaleimide structural unit was 30%, and the molar content of the α -methylstyrene structural unit was 40% based on the total molar amount of each structural unit in the polymer, is shown in table 1.
Preparation example 5
9g of maleic anhydride, 0.7g of azodiisobutyronitrile, 10.62g of alpha-methylstyrene, 1.73g of N-phenylmaleimide and 87.8g of isoamyl butyrate are added into a 500mL three-neck flask, after the materials are uniformly mixed, nitrogen is introduced for 20 minutes, the three-neck flask is moved into a water bath with the temperature of 70 ℃ for reaction for 5 hours, after the reaction is finished, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, and 516.69g of polymer microsphere A is obtained, and the corresponding polymer yield is 75.3 percent. The polymer microsphere size was 2000nm.
Subjecting the polymer microsphere A5 to 1 HNMR measurement, which shows that the molar content of the maleic anhydride structural unit was 50%, the molar content of the N-phenylmaleimide structural unit was 5%, and the molar content of the α -methylstyrene structural unit was 45% based on the total molar amount of each structural unit in the polymer, is shown in table 1.
Preparation example 6
10.1g of maleic anhydride, 0.89g of azodiisobutyronitrile, 4.72g of alpha-methylstyrene, 10.38g of N-phenylmaleimide and 87.8g of isoamyl acetate are added into a 500mL three-necked flask, after the materials are uniformly mixed, nitrogen is introduced into the three-necked flask for 20 minutes, the three-necked flask is moved into a water bath with the temperature of 70 ℃ for reaction for 5 hours, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, and polymer microspheres A617.15g are obtained, and the corresponding polymer yield is 68.9%. The polymer microsphere size was 1800nm.
Subjecting the polymer microsphere A6 to 1 HNMR measurement, in which the molar content of the maleic anhydride structural unit was 52%, the molar content of the N-phenylmaleimide structural unit was 20%, and the molar content of the α -methylstyrene structural unit was 28% based on the total molar amount of each structural unit in the polymer, was carried out, and the results are shown in table 1.
TABLE 1
Polymer microsphere Maleic anhydride/% N-phenylmaleimide/% Alpha-methylstyrene/% Particle size/nm
A1 52 29 19 1500
A2 48 30 22 2000
A3 50 29 21 2400
A4 30 30 40 2500
A5 50 5 45 2000
A6 52 20 28 1800
Examples 1 to 18 and comparative examples 1 to 7
According to the types and the amounts of the components in the heat-resistant light diffusion polypropylene composition shown in Table 2, polypropylene, maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microspheres, silicone resin microspheres and antioxidants were uniformly mixed by a high-speed stirrer, and the addition amounts and proportions are shown in Table 2. And then adding the materials into a double-screw extruder for melt blending and granulating to prepare the heat-resistant light diffusion polypropylene composition, wherein the processing temperature of the screw is 185-215 ℃. The granulated material was subjected to standard injection into test specimens, and the test results are shown in Table 3.
Table 2 (g)
TABLE 3 Table 3
As can be seen from table 2, the polypropylene composition comprising the terpolymer microsphere and the silicone resin microsphere according to the embodiment of the invention has high light transmittance and haze, and can improve the light diffusion performance of the polypropylene material; meanwhile, the heat distortion temperature of the polypropylene composition is obviously improved, and the heat resistance is improved.
In particular, the haze of the polypropylene composition provided in comparative example 3 containing terpolymer microspheres alone was significantly reduced, while the heat distortion temperature of the polypropylene composition provided in comparative example 2 containing silicone resin microspheres alone was significantly reduced. Whereas in comparative example 5, in which the amount of the terpolymer microspheres was excessively large, the transmittance of the resulting polypropylene composition was significantly reduced.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (21)

1. A heat-resistant photodiffusion polypropylene composition, characterized in that the polypropylene composition comprises polypropylene, maleic anhydride/N-phenylmaleimide/α -methylstyrene copolymer microspheres and silicone resin microspheres;
based on 100 parts by weight of polypropylene, the using amount of the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere is 0.3-10 parts by weight, and the using amount of the organosilicon resin microsphere is 0.05-0.5 part by weight;
the sum of the molar contents of the maleic anhydride structural unit, the N-phenylmaleimide structural unit and the alpha-methylstyrene structural unit is 100%;
the particle size of the maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere is 1500-2500nm.
2. The heat-resistant light diffusion polypropylene composition according to claim 1, wherein the maleic anhydride/N-phenylmaleimide/α -methylstyrene copolymer microsphere has a molar content of maleic anhydride structural units of 30 to 52%, a molar content of N-phenylmaleimide structural units of 5 to 30% and a molar content of α -methylstyrene structural units of 20 to 45% based on the total molar amount of each structural unit of the copolymer.
3. The heat-resistant light diffusion polypropylene composition according to claim 1 or 2, wherein the molar content of the maleic anhydride structural unit is 30 to 50%, the molar content of the N-phenylmaleimide structural unit is 5 to 25% and the molar content of the α -methylstyrene structural unit is 20 to 40% based on the total molar amount of each structural unit of the copolymer.
4. The heat resistant light diffusing polypropylene composition of claim 1 or 2, wherein the silicone resin microspheres are organosiloxanes.
5. The heat resistant light diffusion polypropylene composition according to claim 1 or 2, wherein the particle size of the maleic anhydride/N-phenylmaleimide/α -methylstyrene copolymer microspheres is 1500-2000nm.
6. The heat-resistant light diffusion polypropylene composition according to claim 1 or 2, wherein the silicone resin microspheres have a particle size of 0.1-100 μm.
7. The heat resistant light diffusing polypropylene composition according to claim 1 or 2, wherein the silicone resin microspheres have a particle size of 1-50 μm.
8. The heat resistant light diffusing polypropylene composition according to claim 1 or 2, wherein the silicone resin microspheres have a particle size of 1.5-30 μm.
9. The heat resistant light diffusing polypropylene composition of claim 1 or 2, wherein the polypropylene is a polypropylene copolymer.
10. The heat-resistant light diffusion polypropylene composition according to claim 1 or 2, wherein the polypropylene is a random copolymer polypropylene obtained by copolymerizing propylene with an α -olefin.
11. The heat resistant light diffusing polypropylene composition according to claim 1 or 2, wherein the polypropylene has a melt index of 25-60g/min at 230 ℃ and 2.16kg load.
12. The heat resistant light diffusing polypropylene composition of claim 1 or 2, wherein the composition further comprises an antioxidant.
13. The heat-resistant light diffusion polypropylene composition according to claim 12, wherein the antioxidant is 0.1 to 0.5 parts by weight based on 100 parts by weight of polypropylene.
14. The heat-resistant light diffusion polypropylene composition according to claim 12, wherein the antioxidant is 0.2 to 0.5 parts by weight based on 100 parts by weight of polypropylene.
15. A heat-resistant light diffusing polypropylene, characterized in that it is produced from the heat-resistant light diffusing polypropylene composition according to any one of claims 1 to 14.
16. The heat resistant light diffusing polypropylene of claim 15 wherein the light diffusing polypropylene has a heat distortion temperature of T2 and the polypropylene has a heat distortion temperature of T1, T2-T1 ∈0.5 ℃; the light transmittance of the light diffusion polypropylene is more than 70%, and the haze is more than 80%.
17. The heat resistant light diffusing polypropylene of claim 16 wherein T2-T1 is 1.5 ℃ or higher, the light transmittance of the light diffusing polypropylene is greater than 70% and the haze is greater than 85%.
18. The heat resistant light diffusing polypropylene of claim 17, wherein T2-T1 is not less than 3 ℃, the light transmittance of the light diffusing polypropylene is greater than 70%, and the haze is greater than 90%.
19. A process for the preparation of a heat resistant light diffusing polypropylene according to any of claims 15 to 18, wherein said process comprises: the heat-resistant light diffusion polypropylene composition according to any one of claims 1 to 14, which is obtained by melt blending after being uniformly mixed.
20. Use of the heat resistant light diffusing polypropylene composition of any of claims 1-14 or the heat resistant light diffusing polypropylene of any of claims 15-18 in an illuminant.
21. The use of claim 20, wherein the use is in an LED lamp.
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