阅读说明：本技术 一种户外用亚克力光扩散板及其制备方法 (Outdoor acrylic light diffusion plate and preparation method thereof ) 是由 顾祖良 沈小英 于 2021-06-24 设计创作，主要内容包括：本发明公开了一种户外用亚克力光扩散板,包括：聚甲基丙烯酸甲酯60份-80份,无定型透明氟树脂10份-15份,光扩散剂3份-8份,脂肪族二元醇2份-8份,光引发剂1份-5份,交联剂0.1份-1份,其中,所述户外用亚克力光扩散板采用紫外光辐照交联的方法制备所得。本发明利用多种材料自身的优势,进行了有机组合,再通过利用紫外光辐照的方法,在光引发剂和交联剂的作用下,进行迅速复合生成三维网状的交联结构,在交联的过程中,光扩散剂能够较好地分散在其内,避免了传统的光扩散剂在材料的表面容易发生脱落的现象,同时,将无定型透明氟树脂和脂肪族二元醇引入到聚甲基丙烯酸甲酯中,以增强其耐候性,适合于户外使用。(The invention discloses an outdoor acrylic light diffusion plate, which comprises: 60-80 parts of polymethyl methacrylate, 10-15 parts of amorphous transparent fluororesin, 3-8 parts of light diffusant, 2-8 parts of aliphatic diol, 1-5 parts of photoinitiator and 0.1-1 part of cross-linking agent, wherein the outdoor acrylic light diffusion plate is prepared by adopting an ultraviolet irradiation crosslinking method. The invention utilizes the advantages of various materials to carry out organic combination, and then carries out rapid compounding to generate a three-dimensional reticular cross-linking structure under the action of a photoinitiator and a cross-linking agent by utilizing an ultraviolet irradiation method, and the light diffusion agent can be well dispersed in the cross-linking process, thereby avoiding the phenomenon that the traditional light diffusion agent is easy to fall off on the surface of the material.)

1. The outdoor acrylic light diffusion plate is characterized by comprising the following components in parts by weight:

60-80 parts of polymethyl methacrylate, 10-15 parts of amorphous transparent fluororesin, 3-8 parts of light diffusant, 2-8 parts of aliphatic diol, 1-5 parts of photoinitiator and 0.1-1 part of cross-linking agent, wherein the outdoor acrylic light diffusion plate is prepared by adopting an ultraviolet irradiation crosslinking method.

2. The outdoor acryl light diffuser plate according to claim 1, wherein the amorphous transparent fluororesin is one or more than two of a copolymer of tetrafluoroethylene and perfluoro (2, 2-dimethyl-1, 3-dioxole), a copolymer of tetrafluoroethylene and 5-trifluoromethoxy-2, 2, 4-trifluoro-1, 3-dioxole, and a homopolymer of perfluoro (butene-3-yl vinyl ether) which is cyclopolymerized.

3. The outdoor acrylic light diffuser plate according to claim 1, wherein the light diffuser is one or more of nano barium sulfate, calcium carbonate and silicon dioxide.

4. The outdoor acrylic light diffuser plate according to claim 1, wherein the aliphatic diol is 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol.

5. The outdoor acryl light diffuser plate according to claim 1, wherein the photo initiator is one or more of 2, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one.

6. The outdoor acrylic light diffuser plate according to claim 1, wherein the cross-linking agent is one or more of polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, and glycerol ethoxylate dimethacrylate.

7. The outdoor acryl light-diffuser plate as set forth in claim 1, wherein the polymethylmethacrylate is polymethylmethacrylate powder of 80 mesh to 100 mesh.

8. The outdoor acrylic light diffuser plate according to claim 1, wherein the mass ratio of the polymethyl methacrylate, the amorphous transparent fluororesin and the aliphatic diol is 63: 12: (2-4).

9. A method for preparing an outdoor acrylic light diffuser plate as claimed in any one of claims 1 to 8, comprising the steps of:

s1: firstly, uniformly stirring polymethyl methacrylate, amorphous transparent fluororesin and aliphatic diol at normal temperature to obtain premix;

s2: adding a photoinitiator, a cross-linking agent and a light diffusion agent into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: and putting the granules into a finished product extruder, crosslinking and extruding under ultraviolet irradiation to form the outdoor acrylic light diffusion plate.

10. The method of claim 9, wherein the uv light has a wavelength of 200nm to 400nm and a light intensity of 1200mW/cm in step S3²。

Technical Field

The invention relates to the technical field of high polymer materials, in particular to an outdoor acrylic light diffusion plate and a preparation method thereof.

Background

LED is as novel luminescent material, and the wide application is in fields such as automotive lighting, signal indicator, outdoor display screen and indoor outer illumination, nevertheless because LED itself is the pointolite, can produce dazzling, the narrow scheduling problem of illumination area, mainly through increasing the light diffuser plate on the LED lamp at present to solve this problem.

As a commonly used photoelectric display material, the base material of the light diffusion plate is generally a polymer transparent material such as Polycarbonate (PC), polymethyl methacrylate (PMMA), Polystyrene (PS), and the like. Many light diffusion plates with PC as the base material usually need to be added with heat stabilizer and light stabilizer to avoid yellowing of the light diffusion plate caused by thermal oxidation aging and improve the outdoor service life of the light diffusion plate. The PMMA has excellent optical characteristics and ageing resistance, the white light penetrability is as high as 92%, the prepared light diffusion plate has good light penetrability, yellowing and service life reduction caused by ageing can not be caused due to climate change resistance, and the PMMA is particularly suitable for outdoor use.

In the prior art, patent CN107175054B discloses a light diffusion microsphere, which is prepared by preparing a light diffusion material into a microsphere to increase the dispersibility of the light diffusion material in a transparent material. Patent CN103193914B discloses a light diffusing agent, which is prepared by dispersing agent into random copolymer in microsphere structure to increase its thermal stability and dispersibility. However, the preparation process of the method is complex and difficult to control, and is not suitable for large-scale production.

Disclosure of Invention

In order to overcome the defects of the prior art, one of the purposes of the invention is to provide an outdoor acrylic light diffusion plate which has excellent thermal stability and mechanical property, can well disperse a light diffusion agent and is suitable for outdoor use.

The second purpose of the present invention is to provide a method for preparing an outdoor acrylic light diffusion plate, which is simple and easy to control, and can be applied to mass production.

One of the purposes of the invention is realized by adopting the following technical scheme:

an outdoor acrylic light diffusion plate comprises the following components in parts by weight:

60-80 parts of polymethyl methacrylate, 10-15 parts of amorphous transparent fluororesin, 3-8 parts of light diffusant, 2-8 parts of aliphatic diol, 1-5 parts of photoinitiator and 0.1-1 part of cross-linking agent, wherein the outdoor acrylic light diffusion plate is prepared by adopting an ultraviolet irradiation crosslinking method.

The invention utilizes the ultraviolet light irradiation method, under the action of the photoinitiator and the cross-linking agent, a series of macromolecular free radicals generated in photophysical and photochemical processes are generated, the macromolecular free radicals are rapidly compounded to generate a three-dimensional reticular cross-linking structure, the light diffusing agent can be well dispersed in the crosslinking structure in the crosslinking process, the phenomenon that the traditional light diffusing agent is easy to fall off on the surface of the material is avoided, and meanwhile, the amorphous transparent fluororesin and the aliphatic dihydric alcohol are introduced into the polymethyl methacrylate to enhance the weather resistance of the polymethyl methacrylate, so that the invention is suitable for outdoor use.

In addition, the polymethyl methacrylate used in the invention is polymethyl methacrylate powder which is one or two of waste leftover acrylic plate powder and recycled acrylic plate powder, and the particle size of the polymethyl methacrylate powder is 80-100 meshes, so that the environment is protected.

The amorphous transparent fluororesin may be one or more of a copolymer of tetrafluoroethylene and perfluoro (2, 2-dimethyl-1, 3-dioxole), a copolymer of tetrafluoroethylene and 5-trifluoromethoxy-2, 2, 4-trifluoro-1, 3-dioxole, and a cyclopolymerized homopolymer of perfluoro (butene-3-yl vinyl ether). The ring structure in the molecular chain of the amorphous transparent fluororesin has larger steric hindrance effect, the symmetry of the polytetrafluoroethylene is destroyed, a crystal region is difficult to form, the obtained polymer has an amorphous structure and higher optical transparency, and meanwhile, the material keeps the characteristic of thermal stability of the polytetrafluoroethylene.

Further, the light diffusing agent is one or more of nano barium sulfate, calcium carbonate and silicon dioxide.

Further, the aliphatic diol is 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol. 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, which is aliphatic diol, is added into polymethyl methacrylate, so that the glass transition temperature of the material can be obviously improved, and the weather resistance and the transparency can be improved.

Further, the photoinitiator is one or more than two of 2, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propane-1-one.

Further, the cross-linking agent is one or more of polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate and glycerol ethoxylated dimethacrylate.

Further, the mass ratio of the polymethyl methacrylate to the amorphous transparent fluororesin to the aliphatic diol is 63: 12: (2-4).

The second purpose of the invention is realized by adopting the following technical scheme:

a preparation method of an outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate, amorphous transparent fluororesin and aliphatic diol at normal temperature to obtain premix;

s2: adding a photoinitiator, a cross-linking agent, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: and putting the granules into a finished product extruder, crosslinking and extruding under ultraviolet irradiation to form the outdoor acrylic light diffusion plate.

Further, in step S3, the ultraviolet light has a wavelength of 200nm to 400nm and a light intensity of 1200mW/cm²。

Compared with the prior art, the invention has the beneficial effects that:

the outdoor acrylic light diffusion plate disclosed by the invention is organically combined by utilizing the advantages of various materials, and then is quickly compounded to generate a three-dimensional reticular cross-linking structure under the action of a photoinitiator and a cross-linking agent by utilizing an ultraviolet light irradiation method, so that the light diffusion agent can be well dispersed in the cross-linking process, the phenomenon that the traditional light diffusion agent is easy to fall off on the surface of the material is avoided, and meanwhile, amorphous transparent fluororesin and aliphatic dihydric alcohol are introduced into polymethyl methacrylate to enhance the weather resistance of the material, and the outdoor acrylic light diffusion plate is suitable for outdoor use.

The preparation method is simple and easy to control, and can be applied to large-scale production.

Detailed Description

The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.

In the following examples, the aliphatic diol is 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol; the light diffusant is nano barium sulfate; the amorphous transparent fluororesin is a copolymer of tetrafluoroethylene and perfluoro (2, 2-dimethyl-1, 3-dioxole); the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone; the cross-linking agent is polyethylene glycol dimethacrylate, and the polymethyl methacrylate is 80-mesh waste leftover acrylic plate powder. The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.

Example 1

An outdoor acrylic light diffusion plate comprises the following components in parts by weight:

60 parts of polymethyl methacrylate, 10 parts of amorphous transparent fluororesin, 3 parts of light diffusant, 2 parts of aliphatic diol, 1 part of photoinitiator and 0.1 part of crosslinking agent.

The preparation method of the outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate, amorphous transparent fluororesin and aliphatic diol at normal temperature to obtain premix;

s2: adding a photoinitiator, a cross-linking agent, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: placing the granules into a finished product extruder, and extruding at a wavelength of 300nm and a light intensity of 1200mW/cm²Under the irradiation of ultraviolet light, the acrylic light diffusion plate for outdoor use is obtained after cross-linking and extrusion molding.

Example 2

An outdoor acrylic light diffusion plate comprises the following components in parts by weight:

70 parts of polymethyl methacrylate, 12 parts of amorphous transparent fluororesin, 5 parts of light diffusant, 4 parts of aliphatic diol, 3 parts of photoinitiator and 0.5 part of crosslinking agent.

The preparation method of the outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate, amorphous transparent fluororesin and aliphatic diol at normal temperature to obtain premix;

s2: adding a photoinitiator, a cross-linking agent, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: placing the granules into a finished product extruder, and extruding at a wavelength of 300nm and a light intensity of 1200mW/cm²Under the irradiation of ultraviolet light, the acrylic light diffusion plate for outdoor use is obtained after cross-linking and extrusion molding.

Example 3

An outdoor acrylic light diffusion plate comprises the following components in parts by weight:

80 parts of polymethyl methacrylate, 15 parts of amorphous transparent fluororesin, 8 parts of light diffusant, 8 parts of aliphatic diol, 5 parts of photoinitiator and 1 part of crosslinking agent.

The preparation method of the outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate, amorphous transparent fluororesin and aliphatic diol at normal temperature to obtain premix;

s2: adding a photoinitiator, a cross-linking agent, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: placing the granules into a finished product extruder, and extruding at a wavelength of 300nm and a light intensity of 1200mW/cm²Under the irradiation of ultraviolet light, the acrylic light diffusion plate for outdoor use is obtained after cross-linking and extrusion molding.

Example 4

An outdoor acrylic light diffusion plate comprises the following components in parts by weight:

63 parts of polymethyl methacrylate, 12 parts of amorphous transparent fluororesin, 3 parts of light diffusant, 2 parts of aliphatic diol, 1 part of photoinitiator and 0.1 part of crosslinking agent.

The preparation method of the outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate, amorphous transparent fluororesin and aliphatic diol at normal temperature to obtain premix;

s2: adding a photoinitiator, a cross-linking agent, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: placing the granules into a finished product extruder, and extruding at a wavelength of 300nm and a light intensity of 1200mW/cm²Under the irradiation of ultraviolet light, the acrylic light diffusion plate for outdoor use is obtained after cross-linking and extrusion molding.

In the above embodiments, each material is not limited to the above components, and each material may also be composed of other single components or multiple components described in the present invention, and the component parts of each material are not limited to the above parts, and the component parts of each material may also be a combination of other component parts described in the present invention, and are not described herein again.

Comparative example 1

An outdoor acrylic light diffusion plate comprises the following components in parts by weight:

60 parts of polymethyl methacrylate, 3 parts of light diffusant, 2 parts of aliphatic dihydric alcohol, 1 part of photoinitiator and 0.1 part of cross-linking agent.

The preparation method of the outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate and aliphatic dihydric alcohol at normal temperature to obtain a premix;

s2: adding a photoinitiator, a cross-linking agent, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: placing the granules into a finished product extruder, and extruding at a wavelength of 300nm and a light intensity of 1200mW/cm²Under the irradiation of ultraviolet light, the acrylic light diffusion plate for outdoor use is obtained after cross-linking and extrusion molding.

Comparative example 2

An outdoor acrylic light diffusion plate comprises the following components in parts by weight:

60 parts of polymethyl methacrylate, 10 parts of amorphous transparent fluororesin, 3 parts of light diffusant, 1 part of photoinitiator and 0.1 part of crosslinking agent.

The preparation method of the outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate and amorphous transparent fluororesin at normal temperature to obtain premix;

s2: adding a photoinitiator, a cross-linking agent, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: placing the granules into a finished product extruder, and extruding at a wavelength of 300nm and a light intensity of 1200mW/cm²Under the irradiation of ultraviolet light, the acrylic light diffusion plate for outdoor use is obtained after cross-linking and extrusion molding.

Comparative example 3

An outdoor acrylic light diffusion plate comprises the following components in parts by weight:

60 parts of polymethyl methacrylate, 10 parts of amorphous transparent fluororesin, 3 parts of light diffusant, 2 parts of aliphatic diol and 1 part of photoinitiator.

The preparation method of the outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate, amorphous transparent fluororesin and aliphatic diol at normal temperature to obtain premix;

s2: adding a photoinitiator, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: placing the granules into a finished product extruder, and extruding at a wavelength of 300nm and a light intensity of 1200mW/cm²Under the irradiation of ultraviolet light, the acrylic light diffusion plate for outdoor use is obtained after cross-linking and extrusion molding.

Comparative example 4

An outdoor acrylic light diffusion plate comprises the following components in parts by weight:

60 parts of polymethyl methacrylate, 10 parts of amorphous transparent fluororesin, 3 parts of light diffusant, 2 parts of aliphatic diol, 1 part of photoinitiator and 0.1 part of crosslinking agent.

The preparation method of the outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate, amorphous transparent fluororesin and aliphatic diol at normal temperature to obtain premix;

s2: adding a photoinitiator, a cross-linking agent, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: placing the granules into a finished product extruder, and extruding at a wavelength of 300nm and a light intensity of 600mW/cm²Under the irradiation of ultraviolet light, the acrylic light diffusion plate for outdoor use is obtained after cross-linking and extrusion molding.

Comparative example 5

An outdoor acrylic light diffusion plate comprises the following components in parts by weight:

60 parts of polymethyl methacrylate, 10 parts of amorphous transparent fluororesin, 3 parts of light diffusant, 2 parts of aliphatic diol, 1 part of photoinitiator and 0.1 part of crosslinking agent.

The preparation method of the outdoor acrylic light diffusion plate comprises the following preparation steps:

s1: firstly, uniformly stirring polymethyl methacrylate, amorphous transparent fluororesin and aliphatic diol at normal temperature to obtain premix;

s2: adding a photoinitiator, a cross-linking agent, a light stabilizer and a light diffusant into the premix, uniformly stirring, and then putting the mixture into a semi-finished product extruder for extrusion and granulation to obtain granules;

s3: placing the granules into a finished product extruder, and extruding at a wavelength of 300nm and a light intensity of 1800mW/cm²Under the irradiation of ultraviolet light, the acrylic light diffusion plate for outdoor use is obtained after cross-linking and extrusion molding.

Performance testing

The acryl light-diffusing plates manufactured in the above examples 1 to 4 and comparative examples 1 to 5 were subjected to the following performance tests.

1) Light transmittance and haze test

The measurement was carried out using a light transmittance haze meter according to American society for testing and materials Standard ASTM D1003-61(1997) with a test panel thickness of 2m and the following test results.

TABLE 1

Item	Transmittance (a)	Haze/%
			Example 1	86	80
Example 2	87	82
			Example 3	88	85
Example 4	87	83
			Comparative example 1	76	58
Comparative example 2	82	75
			Comparative example 3	79	73
Comparative example 4	73	55
			Comparative example 5	68	52

2) Thermal stability test

The thickness of the sample was 4mm, the xenon lamp ageing time was measured in accordance with GB/T16422.2-1999 and the intensity of the radiation to which the sample was subjected was 350W/cm²±35W/cm²The spectral wavelength of the radiation light is 290-800 nm, the temperature in the box is 65 +/-2 ℃, the relative humidity is 65% +/-5%, the water spraying is continued for 18min, the water spraying interval is 102min, continuous illumination is adopted, the elongation at break of the test sample after the test cannot be lower than 50% of that of the blank sample, and the thermal aging is tested by adopting the GB/T7141 plus 2008 standard, and the results are shown in the following table.

TABLE 2

Item	Xenon lamp aging time/h	Thermal ageing time/h
			Example 1	17600	95000
Example 2	18100	126000
			Example 3	18500	144000
Example 4	19300	165000
			Comparative example 1	6300	26000
Comparative example 2	13200	76500
			Comparative example 3	8100	35000
Comparative example 4	10500	31200
			Comparative example 5	9420	33000

The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.