CN111363109A - Uvioresistant ASA synthetic resin tile - Google Patents
Uvioresistant ASA synthetic resin tile Download PDFInfo
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- CN111363109A CN111363109A CN202010340461.9A CN202010340461A CN111363109A CN 111363109 A CN111363109 A CN 111363109A CN 202010340461 A CN202010340461 A CN 202010340461A CN 111363109 A CN111363109 A CN 111363109A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses an anti-ultraviolet ASA synthetic resin tile, wherein a preparation base material of the tile comprises modified ASA synthetic resin, and the preparation method of the modified ASA synthetic resin comprises the following steps: adding 25-30g of acrylonitrile monomer, 30-40g of styrene monomer, 15-20g of acrylic rubber, 1L of deionized water, 1.5-3g of emulsifier and 3-4g of initiator into a reaction kettle, heating to 60-65 ℃, stirring for carrying out prepolymerization reaction for 15-20min, cooling to room temperature, adding 1-1.5g of emulsifier, 1-2g of initiator, 8.5-10g of block modifier K and 10-20g of acrylonitrile monomer, heating to 75-80 ℃ again, carrying out block polymerization reaction for 2-2.5h, and after the reaction is finished, carrying out emulsion breaking, suction filtration, washing with water and drying to obtain the modified ASA synthetic resin; through an emulsion polymerization method, the prepared block modifier and each monomer of ASA synthetic resin are subjected to block polymerization, hindered amine functional groups and cyclized organic silicon are introduced in a chemical bond mode, a good inhibition effect is achieved on the photo-oxidative degradation reaction of polymers in the resin tiles, and the ultraviolet resistance of the resin tiles is greatly improved.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an ultraviolet-resistant ASA synthetic resin tile.
Background
The tile is an important building material, and is widely applied to self-built houses, high-grade villa houses, park construction, sunlight houses and the like in the rural areas at present, the traditional antique garden building roofs such as the residential building roofs, the building pavilion outlines and the like mostly use the wave tile, also called the small blue tile, the tile is formed by kiln firing after being made into blanks by adopting materials such as clay and the like, and the tile is inevitably provided with some defects due to the characteristics of the materials, the production process and the like: the water absorption is easy, the texture is crisp, and the single block has small installation area, thus leading to high construction cost and maintenance cost. The ASA synthetic resin tile is made of the ultra-high weather-resistant engineering resin ASA by one-step processing by using the most advanced three-layer co-extrusion technology, is a novel environment-friendly roofing material, and is very suitable for' flat slope engineering and villa roofing decoration.
The ASA synthetic resin tile is different from the common resin tile in that the ASA synthetic resin is added; the ASA synthetic resin has good corrosion resistance, water resistance, sound insulation and other properties, but has poor stability to heat and light, and the resin polymer is easy to absorb ultraviolet rays to be oxidized and degraded, generates aging phenomena such as fading, powdering and the like, is not beautiful and has no durability.
Disclosure of Invention
The invention aims to provide an anti-ultraviolet ASA synthetic resin tile, which takes modified ASA synthetic resin as a preparation base material, and carries out block polymerization on a prepared block modifier and all monomers (acrylonitrile monomer, styrene monomer and acrylic rubber) of the ASA synthetic resin by an emulsion polymerization method, and introduces hindered amine functional groups and cyclized organic silicon in a chemical bond mode, so that the anti-ultraviolet performance of the resin tile is greatly improved.
The purpose of the invention can be realized by the following technical scheme:
an uvioresistant ASA synthetic resin tile, the preparation base material of which comprises modified ASA synthetic resin, the preparation method of the modified ASA synthetic resin comprises the following steps:
adding 25-30g of acrylonitrile monomer, 30-40g of styrene monomer, 15-20g of acrylic rubber, 1L of deionized water, 1.5-3g of emulsifier and 3-4g of initiator into a reaction kettle, heating to 60-65 ℃, stirring for carrying out prepolymerization reaction for 15-20min, cooling to room temperature, adding 1-1.5g of emulsifier, 1-2g of initiator, 8.5-10g of block modifier K and 10-20g of acrylonitrile monomer, heating to 75-80 ℃ again, carrying out block polymerization reaction for 2-2.5h, and after the reaction is finished, carrying out demulsification, suction filtration, washing with water and drying to obtain the modified ASA synthetic resin.
Furthermore, the emulsifier is sodium dodecyl benzene sulfonate.
Further, the initiator is one of sodium persulfate, potassium persulfate and ammonium persulfate.
Further, the demulsification is specifically as follows: 100-150ml of methanol and 50ml of saturated saline are added for demulsification.
Further, the preparation method of the block modifier comprises the following steps:
s1, adding 110-120mmol of phenyl maleic anhydride, 100mmol of 4-aminopiperidine, 40ml of anhydrous acetic acid and 300-400ml of solvent tetrahydrofuran into a reaction kettle, heating to 70-75 ℃, carrying out reflux reaction for 10-15h, naturally cooling to room temperature after the reaction is finished, carrying out rotary evaporation to remove the solvent, washing by using anhydrous ether, drying to obtain an amic acid intermediate, adding 500ml of toluene and a catalyst into the obtained amide intermediate, introducing nitrogen to replace air in the reaction kettle, heating to 115-120 ℃, carrying out reflux reaction for 5-6h, carrying out rotary evaporation to remove 1/2-3/4 toluene to obtain a concentrated solution, adding 15% hydrochloric acid aqueous solution, adjusting the pH of the concentrated solution to acidity, adding 150-200ml of ethyl acetate for extraction, removing the solvent by using an organic phase, drying to obtain an intermediate K1;
s2, putting 20-22mmol of intermediate K1 and 10mmol of 2,4, 6-trimethyl-2, 4, 6-trivinylcyclotrisiloxane into a mixer for premixing; adding 200ml of polymerization solvent toluene into a reaction kettle, heating to 115-class 130 ℃, slowly adding a premixed monomer into the reaction kettle, carrying out heat preservation and reflux for 30-40min, then adding an initiator, heating to 200-class 220 ℃, carrying out heat preservation and addition reaction for 25-30min, removing the solvent after the reaction is finished, washing by adopting anhydrous ether, and drying to obtain a block modifier K;
the reaction scheme of the block modifier K is as follows:
further, in step S1, the catalyst is a mixture of 25-30mmol of anhydrous zinc chloride and 25-30mmol of anhydrous aluminum chloride.
Further, in step S1, the step of adjusting the pH of the concentrated solution to be acidic specifically includes: adjusting the pH of the concentrated solution to 1.5-2.0.
Further, in step S2, the initiator is one of di-tert-butyl peroxide and dicumyl peroxide.
The invention has the beneficial effects that:
the invention provides an anti-ultraviolet ASA synthetic resin tile, which takes modified ASA synthetic resin as a preparation base material, block polymerization is carried out on a prepared block modifier and monomers (acrylonitrile monomer, styrene monomer and acrylic rubber) of the ASA synthetic resin by an emulsion polymerization method, a hindered amine functional group is introduced in a chemical bond mode, hindered amine can be converted into nitroxide free radicals under external conditions of light, oxygen and the like, the nitroxide free radicals can capture alkyl, alkoxy and the like generated in the ASA synthetic resin due to degradation, corresponding ester and peroxyester are generated, the ester and the peroxyester can react with alkyl, alkoxy or peroxyalkyl, the nitroxide free radicals are generated while the free radicals are eliminated, and the cycle reaction can sustainably and durably maintain the anti-ultraviolet performance of the resin tile, so that the aging of the resin tile is slowed down;
in addition, cyclic organic silicon is introduced into the modified ASA synthetic resin, and the high bond of the silicone-grease bond can improve the heat resistance of the ASA synthetic resin, so that the high temperature resistance of the resin tile is improved, a good inhibition effect on the photo-oxidative degradation reaction of polymers in the resin tile is achieved, and the ultraviolet resistance of the resin tile is further improved.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the block modifier comprises the following steps:
s1, adding 110-120mmol of phenyl maleic anhydride, 100mmol of 4-aminopiperidine, 40ml of anhydrous acetic acid and 300-400ml of solvent tetrahydrofuran into a reaction kettle, heating to 70-75 ℃, carrying out reflux reaction for 10-15h, naturally cooling to room temperature after the reaction is finished, carrying out rotary evaporation to remove the solvent, washing by using anhydrous ether, drying to obtain an amic acid intermediate, adding 500ml of toluene, 25-30mmol of anhydrous zinc chloride and 25-30mmol of anhydrous aluminum chloride into the obtained amide intermediate, introducing nitrogen to replace air in the reaction kettle, heating to 115-120 ℃, carrying out reflux reaction for 5-6h, carrying out rotary evaporation to remove 1/2-3/4 toluene to obtain a concentrated solution, adding 15% hydrochloric acid aqueous solution, adjusting the pH of the concentrated solution to 1.5-2.0, then adding 150-200ml of ethyl acetate for extraction, removing the solvent from the organic phase, and drying to obtain an intermediate K1;
the mass spectrum result of the obtained intermediate K1 is as follows: HRMS m/z (ESI)+)calcd for C15H16N2O2([M+1]),257.3013；
S2, putting 20-22mmol of intermediate K1 and 10mmol of 2,4, 6-trimethyl-2, 4, 6-trivinylcyclotrisiloxane into a mixer for premixing; adding 200ml of polymerization solvent toluene into a reaction kettle, heating to 115-phase 130 ℃, slowly adding a premixed monomer into the reaction kettle, carrying out heat preservation and reflux for 30-40min, then adding an initiator (di-tert-butyl peroxide and dicumyl peroxide), heating to 200-phase 220 ℃, carrying out heat preservation and addition reaction for 25-30min, removing the solvent after the reaction is finished, washing by adopting anhydrous ether, and drying to obtain a block modifier K; the reaction scheme of the block modifier K is as follows:
the mass spectrum result of the obtained block modifier K is as follows: HRMS m/z (ESI)+)calcd for C39H50N4O7Si3([M+1]),771.0903。
Example 2
An uvioresistant ASA synthetic resin tile, the preparation base material of which comprises modified ASA synthetic resin, the preparation method of the modified ASA synthetic resin comprises the following steps:
adding 25g of acrylonitrile monomer, 35g of styrene monomer, 15g of acrylic rubber, 1L of deionized water, 2g of emulsifier sodium dodecyl benzene sulfonate and 3g of initiator sodium persulfate into a reaction kettle, heating to 60 ℃, stirring for carrying out prepolymerization reaction for 15min, cooling to room temperature, then adding 1g of emulsifier sodium dodecyl benzene sulfonate, 1g of initiator sodium persulfate, 9g of block modifier K and 15g of acrylonitrile monomer, heating to 75 ℃ again, carrying out block polymerization reaction for 2h, adding 100ml of methanol and 50ml of saturated salt water after the reaction is finished, carrying out emulsion breaking, carrying out suction filtration, washing and drying, and obtaining the modified ASA synthetic resin.
Example 3
An uvioresistant ASA synthetic resin tile, the preparation base material of which comprises modified ASA synthetic resin, the preparation method of the modified ASA synthetic resin comprises the following steps:
adding 30g of acrylonitrile monomer, 40g of styrene monomer, 17g of acrylic rubber, 1L of deionized water, 3g of emulsifier sodium dodecyl benzene sulfonate and 3g of initiator sodium persulfate into a reaction kettle, heating to 65 ℃, stirring for carrying out prepolymerization reaction for 20min, cooling to room temperature, then adding 1g of emulsifier sodium dodecyl benzene sulfonate, 2g of initiator sodium persulfate, 8.5g of block modifier K and 10g of acrylonitrile monomer, heating to 80 ℃ again, carrying out block polymerization reaction for 2.5h, after the reaction is finished, adding 150ml of methanol and 50ml of saturated salt water for demulsification, and carrying out suction filtration, washing and drying to obtain the modified ASA synthetic resin.
Example 4
An uvioresistant ASA synthetic resin tile, the preparation base material of which comprises modified ASA synthetic resin, the preparation method of the modified ASA synthetic resin comprises the following steps:
adding 27g of acrylonitrile monomer, 30g of styrene monomer, 20g of acrylic rubber, 1L of deionized water, 2.5g of emulsifier sodium dodecyl benzene sulfonate and 3.5g of initiator sodium persulfate into a reaction kettle, heating to 60 ℃, stirring for carrying out prepolymerization reaction for 20min, cooling to room temperature, then adding 1g of emulsifier sodium dodecyl benzene sulfonate, 2g of initiator sodium persulfate, 10g of block modifier K and 15g of acrylonitrile monomer, heating to 80 ℃ again, carrying out block polymerization reaction for 2h, adding 120ml of methanol and 50ml of saturated salt water after the reaction is finished, carrying out demulsification, carrying out suction filtration, washing and drying to obtain the modified ASA synthetic resin.
Comparative example 1
And carrying out mechanical melting and mixing on the ASA synthetic resin and a block modifier K to prepare the modified ASA synthetic resin.
Performance testing of the newly prepared modified ASA synthetic resin
The modified ASA synthetic resins prepared in examples 2 to 4 and comparative example 1 were rinsed with water at a temperature of 40 to 45 c for 5 days, and then continuously irradiated with a deuterium lamp for one month, with the following test results:
the experiments show that the block modifier and the monomers (acrylonitrile monomer, styrene monomer and acrylic rubber) of the ASA synthetic resin are subjected to block polymerization, hindered amine functional groups and organic silicon are introduced in a chemical bond mode and firmly connected in the ASA synthetic resin, the surface is not easy to separate out, and the resin tile can be kept from being oxidized for a long time.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (8)
1. An uvioresistant ASA synthetic resin tile is characterized in that: the preparation base material comprises modified ASA synthetic resin, and the preparation method of the modified ASA synthetic resin comprises the following steps:
adding 25-30g of acrylonitrile monomer, 30-40g of styrene monomer, 15-20g of acrylic rubber, 1L of deionized water, 1.5-3g of emulsifier and 3-4g of initiator into a reaction kettle, heating to 60-65 ℃, stirring for carrying out prepolymerization reaction for 15-20min, cooling to room temperature, adding 1-1.5g of emulsifier, 1-2g of initiator, 8.5-10g of block modifier K and 10-20g of acrylonitrile monomer, heating to 75-80 ℃ again, carrying out block polymerization reaction for 2-2.5h, and after the reaction is finished, carrying out demulsification, suction filtration, washing with water and drying to obtain the modified ASA synthetic resin.
2. The ultraviolet resistant ASA synthetic resin tile as set forth in claim 1, wherein: the emulsifier is sodium dodecyl benzene sulfonate.
3. The ultraviolet resistant ASA synthetic resin tile as set forth in claim 1, wherein: the initiator is one of sodium persulfate, potassium persulfate and ammonium persulfate.
4. The ultraviolet resistant ASA synthetic resin tile as set forth in claim 1, wherein: the demulsification is specifically as follows: 100-150ml of methanol and 50ml of saturated saline are added for demulsification.
5. The ultraviolet resistant ASA synthetic resin tile as set forth in claim 1, wherein: the preparation method of the block modifier comprises the following steps:
s1, adding 110-120mmol of phenyl maleic anhydride, 100mmol of 4-aminopiperidine, 40ml of anhydrous acetic acid and 300-400ml of solvent tetrahydrofuran into a reaction kettle, heating to 70-75 ℃, carrying out reflux reaction for 10-15h, naturally cooling to room temperature after the reaction is finished, carrying out rotary evaporation to remove the solvent, washing by using anhydrous ether, drying to obtain an amic acid intermediate, adding 500ml of toluene and a catalyst into the obtained amide intermediate, introducing nitrogen to replace air in the reaction kettle, heating to 115-120 ℃, carrying out reflux reaction for 5-6h, carrying out rotary evaporation to remove 1/2-3/4 toluene to obtain a concentrated solution, adding 15% hydrochloric acid aqueous solution, adjusting the pH of the concentrated solution to acidity, adding 150-200ml of ethyl acetate for extraction, removing the solvent by using an organic phase, drying to obtain an intermediate K1;
s2, putting 20-22mmol of intermediate K1 and 10mmol of 2,4, 6-trimethyl-2, 4, 6-trivinylcyclotrisiloxane into a mixer for premixing; adding 200ml of polymerization solvent toluene into a reaction kettle, heating to 115-class 130 ℃, slowly adding a premixed monomer into the reaction kettle, carrying out heat preservation and reflux for 30-40min, then adding an initiator, heating to 200-class 220 ℃, carrying out heat preservation and addition reaction for 25-30min, removing the solvent after the reaction is finished, washing by adopting anhydrous ether, and drying to obtain a block modifier K;
the reaction scheme of the block modifier K is as follows:
6. the ultraviolet resistant ASA synthetic resin tile as set forth in claim 5, wherein: in step S1, the catalyst is a mixture of 25-30mmol of anhydrous zinc chloride and 25-30mmol of anhydrous aluminum chloride.
7. The ultraviolet resistant ASA synthetic resin tile as set forth in claim 5, wherein: in step S1, the specific step of adjusting the pH of the concentrated solution to acidic is: adjusting the pH of the concentrated solution to 1.5-2.0.
8. The ultraviolet resistant ASA synthetic resin tile as set forth in claim 5, wherein: in step S2, the initiator is one of di-tert-butyl peroxide and dicumyl peroxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010340461.9A CN111363109A (en) | 2020-04-26 | 2020-04-26 | Uvioresistant ASA synthetic resin tile |
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| CN202010340461.9A CN111363109A (en) | 2020-04-26 | 2020-04-26 | Uvioresistant ASA synthetic resin tile |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724628A (en) * | 2020-11-10 | 2021-04-30 | 北京腾燊科技有限公司 | Wind power blade sawtooth tail edge material based on intrinsic aging-resistant polymer |
| WO2024212314A1 (en) * | 2023-04-13 | 2024-10-17 | 山东万达化工有限公司 | Asa resin and preparation method therefor |
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| US20030153710A1 (en) * | 2001-07-04 | 2003-08-14 | Yang-Hyun Shin | Method for preparing of weatherability thermoplastic resin |
| CN103242478A (en) * | 2013-05-17 | 2013-08-14 | 合肥工业大学 | Acrylate agglomerant and preparation method thereof, and method for modifying ASA (acrylonitrile-styrene-acrylate) resin with agglomerant |
| CN106283655A (en) * | 2016-08-22 | 2017-01-04 | 浙江西大门新材料股份有限公司 | A kind of preparation method of uvioresistant polyacrylate dispersion |
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2020
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030153710A1 (en) * | 2001-07-04 | 2003-08-14 | Yang-Hyun Shin | Method for preparing of weatherability thermoplastic resin |
| CN103242478A (en) * | 2013-05-17 | 2013-08-14 | 合肥工业大学 | Acrylate agglomerant and preparation method thereof, and method for modifying ASA (acrylonitrile-styrene-acrylate) resin with agglomerant |
| CN106283655A (en) * | 2016-08-22 | 2017-01-04 | 浙江西大门新材料股份有限公司 | A kind of preparation method of uvioresistant polyacrylate dispersion |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724628A (en) * | 2020-11-10 | 2021-04-30 | 北京腾燊科技有限公司 | Wind power blade sawtooth tail edge material based on intrinsic aging-resistant polymer |
| CN112724628B (en) * | 2020-11-10 | 2024-03-26 | 宁波腾燊科技发展有限公司 | Wind power blade sawtooth trailing edge material based on intrinsic aging-resistant polymer |
| WO2024212314A1 (en) * | 2023-04-13 | 2024-10-17 | 山东万达化工有限公司 | Asa resin and preparation method therefor |
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Application publication date: 20200703 |