CN112175393A - Scratch-resistant agent for highlight spray-free PMMA and preparation method thereof - Google Patents
Scratch-resistant agent for highlight spray-free PMMA and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08K9/00—Use of pretreated ingredients
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Abstract
The invention discloses a scratch-resistant agent for highlight spray-free PMMA and a preparation method thereof, wherein the scratch-resistant agent for highlight spray-free PMMA comprises the following components: 40-70 parts of nano zirconium dioxide; 10-30 parts of modified polysiloxane; 20-50 parts of long-chain alkyl polysiloxane. The invention also discloses a scratch-resistant PMMA composite material. The scratch-resistant agent can effectively improve the scratch resistance of the PMMA surface, has high long-term stability, enables a workpiece to keep long-term excellent surface glossiness, and can effectively improve other comprehensive performances such as demoulding of PMMA.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-gloss spray-free PMMA scratch-resistant agent and a preparation method thereof.
Background
Polymethyl methacrylate (PMMA) is a highly transparent amorphous thermoplastic polymer, is the most excellent high-molecular transparent material at present, has high mechanical strength and good weather resistance, and is widely applied to the fields of optical materials, medicine, automobiles, electric appliances and the like, but PMMA has low surface hardness, is easy to scratch and scratch by hard objects to lose luster, has poor scratch resistance and obviously influences the appearance of a finished piece. With the development of the spray-free technology, the high-gloss spray-free PMMA is more applied to surface decoration of products, such as automobile grids, columns and other parts, and has better aesthetic property, so that the requirement on the scratch resistance of the surface is higher. The traditional method is to paint the PMMA surface, and the scratch resistance of the PMMA surface is improved by improving the surface hardness, but the paint has the problems of complex process, high cost, environmental pollution, surface defects caused by secondary processing and the like.
Chinese patent application CN111154210A uses silicone based scratch resistant agents and silicone rubber to improve the scratch resistance of PMMA materials. The Chinese patent application CN109401161A uses fluororesin and silicone powder as a composite scratch resistant agent to improve the scratch resistance of PMMA material. The Chinese patent application CN110256798A uses nano zirconium dioxide and silicone master batch to respectively improve the surface hardness and the scratch resistance of PMMA/ASA alloy. The silicone is a common scratch-resistant agent, and generally improves the scratch resistance of materials by reducing the friction coefficient, and the common silicone scratch-resistant agent has poor compatibility with the materials and can reduce the surface glossiness of high-gloss materials. Therefore, the organic silicon is subjected to compatibility modification and is cooperated with the surface hardness modifier, so that the scratch resistance of PMMA can be greatly improved from the aspects of reducing the surface friction coefficient and improving the surface hardness, and the surface glossiness can not be reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a scratch-resistant agent for highlight spray-free PMMA (polymethyl methacrylate), which can effectively improve the scratch resistance of the surface of PMMA, has high long-term stability, keeps the long-term excellent surface glossiness of a workpiece, and can effectively improve the performances of demoulding of PMMA and the like.
In addition, the invention also provides a preparation method of the scratch-resistant agent for the highlight spray-free PMMA, the preparation method is simple to operate, the process conditions are mild, and the prepared scratch-resistant agent is good in stability and convenient to use.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the scratch-resistant agent for the high-gloss spray-free PMMA comprises the following components in parts by weight:
40-70 parts of nano zirconium dioxide;
10-30 parts of modified polysiloxane;
20-50 parts of long-chain alkyl polysiloxane.
As a preferable technical scheme, the nano zirconium dioxide is treated by a silane coupling agent or is nano zirconium dioxide dispersion liquid, wherein the mass part of the nano zirconium dioxide is more than 99 percent; wherein the mass fraction refers to the dry-based purity.
As a preferred technical solution, the modified polysiloxane is a polyester modified polysiloxane, and the structure thereof is:
as a preferred embodiment, the long-chain alkyl polysiloxane has the following structural formula, wherein n is greater than 30:
in order to solve another technical problem, the technical scheme adopted by the invention is as follows:
a preparation method of a scratch-resistant agent for highlight spray-free PMMA comprises the following steps:
(1) weighing modified polysiloxane and long-chain alkyl polysiloxane, adding the modified polysiloxane and the long-chain alkyl polysiloxane into a stirring kettle, heating and melting, and stirring for 20-40 min after all the components are melted to prepare a molten material;
(2) weighing nanometer zirconium dioxide, slowly adding the nanometer zirconium dioxide into the molten material, and continuously stirring and mixing for 60-120 min after all the nanometer zirconium dioxide is added to obtain a premix;
(3) and taking out the premix, cooling the premix into a flaky solid through a steel belt with cooling water, grinding the flaky solid through a grinding machine, sieving, weighing and packaging to obtain the scratch-resistant agent.
As a preferable technical scheme, in the steps (1) and (2), the temperature during melt blending is 100-120 ℃.
As a preferable technical scheme, in the step (3), the size of the screen in the filtering process is 6-10 meshes.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a scratch resistant PMMA composite comprising the following components: polymethyl methacrylate (PMMA) and scratch resistance; the scratch-resistant agent is the scratch-resistant agent for the high-gloss spray-free PMMA.
As a preferable technical scheme, the scratch-resistant PMMA composite material also comprises high-gloss black master batch and an antioxidant.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the nano zirconium dioxide has high hardness, good wear resistance and good dispersibility, can be uniformly distributed in PMMA, and improves the surface hardness of PMMA, so that the scratch resistance of PMMA is effectively improved, and meanwhile, the zirconium dioxide has high toughness and can also enhance the mechanical property of PMMA; the polyester modified polysiloxane has excellent compatibility of polyester and PMMA, and lubricating property, mold release property and low friction coefficient of the polysiloxane; the long-chain alkyl polysiloxane has better performance than polyester modified polysiloxane, and the two modified polysiloxanes act synergistically to further improve the compatibility of the polysiloxane and PMMA and reduce the surface friction coefficient of PMMA, so that the scratch resistance and the demolding property of PMMA are improved.
The scratch-resistant agent consists of nano zirconium dioxide, modified polysiloxane and long-chain alkyl polysiloxane, improves the scratch-resistant performance of PMMA in the aspects of improving the surface hardness of PMMA and reducing the surface friction coefficient, and eliminates the phenomenon of stress concentration and whitening caused by scraping; moreover, the modified zirconium dioxide and polysiloxane have good compatibility with PMMA, good dispersibility, long-acting stability and long-term excellent surface gloss of PMMA.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which are provided for the purpose of illustration only and are not intended to be limiting.
The nano zirconium dioxide used in the following examples is VK-R30 (used after self-treatment with silane coupling agent) produced by new materials of cheng crystal rui, inc; the modified polysiloxane is polyester modified polysiloxane SG-600A produced by Zhejiang Jiahua refinement Limited company; the long-chain alkyl polysiloxane is SG-655 produced by Jiangzhou Jiahua refined products company Limited; the highlight black master batch is PAB 140 produced by Shanghai Jazz minister commercial and trade Co., Ltd, and the antioxidant is Irganox 1010 produced by Swiss Ciba Fine chemical Co., Ltd; PMMA is MF-001 produced by Mitsubishi chemical polymer materials (Nantong) Co., Ltd and CM-211 produced by Zhenjiang beauty works Co., Ltd.
Example 1
The scratch-resistant agent for the high-gloss spray-free PMMA comprises the following components in parts by weight: 50 parts of nano zirconium dioxide; 15 parts of modified polysiloxane; 35 parts of long-chain alkyl polysiloxane.
The preparation method comprises the following steps: weighing modified polysiloxane and long-chain alkyl polysiloxane according to a proportion, melting in a melting kettle at 100-120 ℃, mixing for 30min, adding nano zirconium dioxide, stirring and mixing for 60min to obtain a mixed material; and (3) cooling the mixed material by a steel belt with cooling water, grinding the mixed material into powder, and sieving the powder by a 6-mesh sieve to obtain a finished product of the scratch-resistant agent.
A PMMA composite material is prepared by uniformly mixing 3 parts by weight of the scratch-resistant agent prepared in the example 1, 1 part by weight of highlight black master batch, 0.3 part by weight of antioxidant and Mitsubishi PMMA MF-001 in a stirrer, then carrying out melt blending extrusion in a double-screw extruder at the extrusion temperature of 210-230 ℃ and the screw rotation speed of 180rpm, and carrying out granulation and drying to obtain the scratch-resistant PMMA granules.
Example 2
The scratch-resistant agent for the high-gloss spray-free PMMA comprises the following components in parts by weight: 50 parts of nano zirconium dioxide; 20 parts of modified polysiloxane; 30 parts of long-chain alkyl polysiloxane.
The preparation method comprises the following steps: weighing modified polysiloxane and long-chain alkyl polysiloxane according to a proportion, melting in a melting kettle at 100-120 ℃, mixing for 30min, adding nano zirconium dioxide, stirring and mixing for 60min to obtain a mixed material; and (3) cooling the mixed material by a steel belt with cooling water, grinding the mixed material into powder, and sieving the powder by a 6-mesh sieve to obtain a finished product of the scratch-resistant agent.
A PMMA composite material is prepared by uniformly mixing 3 parts by weight of the scratch-resistant agent prepared in the embodiment 2, 1 part by weight of highlight black master batch, 0.3 part by weight of antioxidant and Mitsubishi PMMA MF-001 in a stirrer, then carrying out melt blending extrusion in a double-screw extruder at the extrusion temperature of 210-230 ℃ and the screw rotation speed of 180rpm, and carrying out granulation and drying to obtain the scratch-resistant PMMA granules.
Example 3
The scratch-resistant agent for the high-gloss spray-free PMMA comprises the following components in parts by weight: 40 parts of nano zirconium dioxide; 20 parts of modified polysiloxane; 40 parts of long-chain alkyl polysiloxane.
The preparation method comprises the following steps: weighing modified polysiloxane and long-chain alkyl polysiloxane according to a proportion, melting in a melting kettle at 100-120 ℃, mixing for 30min, adding nano zirconium dioxide, stirring and mixing for 60min to obtain a mixed material; and (3) cooling the mixed material by a steel belt with cooling water, grinding the mixed material into powder, and sieving the powder by a 6-mesh sieve to obtain a finished product of the scratch-resistant agent.
A PMMA composite material is prepared by uniformly mixing 3 parts by weight of the scratch-resistant agent prepared in the embodiment 3, 1 part by weight of highlight black master batch, 0.3 part by weight of antioxidant and Mitsubishi PMMA MF-001 in a stirrer, then carrying out melt blending extrusion in a double-screw extruder at the extrusion temperature of 210-230 ℃ and the screw rotation speed of 180rpm, and carrying out granulation and drying to obtain the scratch-resistant PMMA granules.
Comparative example 1
The scratch-resistant agent for the high-gloss spray-free PMMA comprises the following components in parts by weight: 60 parts of nano zirconium dioxide; 40 parts of common silicone oil.
The preparation method comprises the following steps: weighing the raw materials in proportion, and uniformly mixing in a high-speed mixer for 10min to obtain the compound ingredient.
A PMMA composite material is prepared by uniformly mixing 3 parts by weight of a compound material prepared in the comparative example 1, 1 part by weight of highlight black sand, 0.3 part by weight of an antioxidant and Mitsubishi PMMA MF-001 in a stirrer, then carrying out melt blending extrusion in a double-screw extruder at the extrusion temperature of 210-230 ℃ and the screw rotation speed of 180rpm, and carrying out granulation and drying to obtain the scratch-resistant PMMA granules.
Comparative example 2
The scratch-resistant agent for the high-gloss spray-free PMMA comprises the following components in parts by weight: 50 parts of nano zirconium dioxide; 50 parts of ultrahigh molecular weight polysiloxane (molecular weight 60 ten thousand).
The preparation method comprises the following steps: weighing the raw materials in proportion, and intermittently and uniformly mixing in a high-speed mixer for 10min to obtain the compound material.
3 parts of the compound material prepared in the comparative example 2, 1 part of highlight black sand, 0.3 part of antioxidant and Mitsubishi PMMA MF-001 are uniformly mixed in a stirrer, then are melted, blended and extruded in a double-screw extruder, the extrusion temperature is 210-230 ℃, the screw rotation speed is 180rpm, and the scratch-resistant PMMA granular material is obtained after the granular material is cut and dried.
Example 4
The scratch-resistant agent for the high-gloss spray-free PMMA comprises the following components in parts by weight: 50 parts of nano zirconium dioxide; 15 parts of modified polysiloxane; 35 parts of long-chain alkyl polysiloxane.
The preparation method comprises the following steps: weighing modified polysiloxane and long-chain alkyl polysiloxane according to a proportion, melting in a melting kettle at 100-120 ℃, mixing for 30min, adding nano zirconium dioxide, stirring and mixing for 60min to obtain a mixed material; and (3) cooling the mixed material by a steel belt with cooling water, grinding the mixed material into powder, and sieving the powder by a 6-mesh sieve to obtain a finished product of the scratch-resistant agent.
A PMMA composite material is prepared by uniformly mixing 3 parts by weight of the scratch-resistant agent prepared in the embodiment 4, 1 part by weight of highlight black master batch, 0.3 part by weight of antioxidant and Qimei PMMA CM-211 in a stirrer, then carrying out melt blending extrusion in a double-screw extruder, carrying out extrusion at the temperature of 210-240 ℃ at the screw rotation speed of 180rpm, carrying out granulation and drying to obtain the scratch-resistant PMMA granules.
Example 5
The scratch-resistant agent for the high-gloss spray-free PMMA comprises the following components in parts by weight: 50 parts of nano zirconium dioxide; 20 parts of modified polysiloxane; 30 parts of long-chain alkyl polysiloxane.
The preparation method comprises the following steps: weighing modified polysiloxane and long-chain alkyl polysiloxane according to a proportion, melting in a melting kettle at 100-120 ℃, mixing for 30min, adding nano zirconium dioxide, stirring and mixing for 60min to obtain a mixed material; and (3) cooling the mixed material by a steel belt with cooling water, grinding the mixed material into powder, and sieving the powder by a 6-mesh sieve to obtain a finished product of the scratch-resistant agent.
A PMMA composite material is prepared by uniformly mixing 3 parts by weight of the scratch-resistant agent prepared in the embodiment 5, 1 part by weight of highlight black master batch, 0.3 part by weight of antioxidant and Qimei PMMA CM-211 in a stirrer, then carrying out melt blending extrusion in a double-screw extruder, carrying out extrusion at the temperature of 210-240 ℃ at the screw rotation speed of 180rpm, carrying out granulation and drying to obtain the scratch-resistant PMMA granules.
Example 6
The scratch-resistant agent for the high-gloss spray-free PMMA comprises the following components in parts by weight: 40 parts of nano zirconium dioxide; 20 parts of modified polysiloxane; 40 parts of long-chain alkyl polysiloxane.
The preparation method comprises the following steps: weighing modified polysiloxane and long-chain alkyl polysiloxane according to a proportion, melting in a melting kettle at 100-120 ℃, mixing for 30min, adding nano zirconium dioxide, stirring and mixing for 60min to obtain a mixed material; and (3) cooling the mixed material by a steel belt with cooling water, grinding the mixed material into powder, and sieving the powder by a 6-mesh sieve to obtain a finished product of the scratch-resistant agent.
A PMMA composite material is prepared by uniformly mixing 3 parts by weight of the scratch-resistant agent prepared in the embodiment 6, 1 part by weight of highlight black master batch, 0.3 part by weight of antioxidant and Qimei PMMA CM-211 in a stirrer, then carrying out melt blending extrusion in a double-screw extruder, carrying out extrusion at the temperature of 210-240 ℃ at the screw rotation speed of 180rpm, carrying out granulation and drying to obtain the scratch-resistant PMMA granules.
And (3) carrying out performance test on the prepared scratch-resistant PMMA composite material.
The scratch-resistant PMMA composite materials prepared in comparative examples 1-2 and examples 1-6, Mitsubishi PMMA MF-001 (marked as blank 1) and Mitsubishi PMMA CM-211 (marked as blank 2) were respectively injection-molded into 150 × 3mm specification highlight sample plates to be used as test samples for performance test.
1. Scratch resistance
The scratch resistance test is carried out according to the GMW14688 standard, the instrument is a German Erichsen 430P grid scratch instrument, the scratch finger is 1.0mm, the scratch speed is 1m/min, and the load is 20N.
2. Hardness of pencil
The pencil hardness test is carried out according to the GB/T6739-2006 standard.
3. Surface gloss
The surface gloss test was carried out according to GB/T8807-1988 using a 3nh model YG268 gloss meter at a test angle of 60 ℃ and the average was taken at 5 points on the panel test.
The test results are shown in table 1:
TABLE 1
Note: the more major ═ is, the more severe the scratch whitening is, the more minor the stress whitening is, the more the whitening is, the less stress whitening is, the better the performance is, and the higher the gloss value is, the better the gloss is.
From the test results, the scratch resistance of PMMA is improved to a certain extent by adding common silicone oil, but the scratch resistance of PMMA is obviously reduced because the scratch resistance of PMMA is poor due to the low molecular weight and poor compatibility with PMMA, and the scratch resistance is separated out to the surface and shows a fogging phenomenon. The addition of the ultra-high molecular weight polysiloxane further improves the scratch resistance of PMMA, and similarly, since the compatibility with PMMA is not good, the dispersion is not uniform on the surface, resulting in a decrease in gloss. The modified polysiloxane improves the compatibility and the dispersibility with PMMA, keeps the original glossiness, and simultaneously improves the scratch resistance of PMMA together with the synergistic effect of nano zirconium dioxide.
Although specific embodiments of the invention have been described, many other forms and modifications of the invention will be apparent to those skilled in the art. It is to be understood that the appended claims and this invention generally cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
Claims (9)
1. The scratch-resistant agent for the high-gloss spray-free PMMA is characterized by comprising the following components in parts by weight:
40-70 parts of nano zirconium dioxide;
10-30 parts of modified polysiloxane;
20-50 parts of long-chain alkyl polysiloxane.
2. The scratch-resistant agent for highlight free-spraying PMMA according to claim 1 is characterized in that the nano zirconium dioxide is nano zirconium dioxide treated by silane coupling agent or nano zirconium dioxide dispersion liquid; wherein the nanometer zirconium dioxide comprises more than 99 percent of nanometer zirconium dioxide by mass.
3. The scratch-resistant agent for high-gloss spray-free PMMA according to claim 1, characterized in that the modified polysiloxane is polyester modified polysiloxane, the structure of which is as follows:
4. the scratch-resistant agent for high gloss spray-free PMMA according to claim 1, characterized in that the long-chain alkyl polysiloxane has the following structural formula:
wherein n is greater than 30.
5. The process for the preparation of a scratch-resistant agent for high gloss spray-free PMMA according to any of claims 1 to 4, characterized by comprising the following steps:
(1) weighing modified polysiloxane and long-chain alkyl polysiloxane, adding the modified polysiloxane and the long-chain alkyl polysiloxane into a stirring kettle, heating and melting, and stirring for 20-40 min after all the components are melted to prepare a molten material;
(2) weighing nanometer zirconium dioxide, slowly adding the nanometer zirconium dioxide into the molten material, and continuously stirring and mixing for 60-120 min after all the nanometer zirconium dioxide is added to obtain a premix;
(3) and taking out the premix, cooling the premix into a flaky solid through a steel belt with cooling water, grinding the flaky solid through a grinding machine, sieving, weighing and packaging to obtain the scratch-resistant agent.
6. The method for preparing the scratch resistant agent for high gloss spray-free PMMA according to the claim 5, characterized in that the temperature of the melt blending in the steps (1) and (2) is 100-120 ℃.
7. The method for preparing the scratch resistant agent for high gloss spray-free PMMA according to claim 5, characterized in that in the step (3), the size of the screen mesh in the filtering process is 6-10 meshes.
8. The scratch-resistant PMMA composite material is characterized by comprising the following components:
polymethyl methacrylate (PMMA);
a scratch-resistant agent;
wherein the scratch-resistant agent is the scratch-resistant agent for the high-gloss spray-free PMMA according to any one of claims 1 to 7.
9. The scratch resistant PMMA composite of claim 8 further including a high gloss black masterbatch and an antioxidant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116218115A (en) * | 2022-12-27 | 2023-06-06 | 金发科技股份有限公司 | PMMA alloy material and preparation method and application thereof |
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