CN109400789B - Preparation method of acrylic copolymer for reflective film - Google Patents
Preparation method of acrylic copolymer for reflective film Download PDFInfo
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- CN109400789B CN109400789B CN201811189287.1A CN201811189287A CN109400789B CN 109400789 B CN109400789 B CN 109400789B CN 201811189287 A CN201811189287 A CN 201811189287A CN 109400789 B CN109400789 B CN 109400789B
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- 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
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract
The invention discloses a preparation method of an acrylic copolymer for a reflective film, which comprises the following steps: (1) weighing a soft monomer, a hard monomer, a functional monomer, a long carbon chain monomer, an initiator and a solvent, and preparing to form a mixture A; (2) putting the mixture A into a reaction vessel and stirring; (3) continuously inputting nitrogen into the reaction vessel; (4) stopping nitrogen input and increasing the temperature in the reaction vessel; (5) weighing a soft monomer, a hard monomer, a functional monomer, a long carbon chain monomer, an initiator and a solvent, and preparing to form a mixture B; (6) dropwise adding the mixture B into a reaction container; (7) weighing an initiator and a solvent to form a mixture C, and dropwise adding the mixture C into a reaction container; (8) the solvent was weighed and charged into the reaction vessel, followed by lowering the temperature and stopping the machine to pour out the acrylic copolymer. The acrylic copolymer prepared by the steps has stronger chemical resistance, good tensile strength and better low-temperature flexibility.
Description
Technical Field
The invention relates to the technical field of reflective materials, in particular to a preparation method of an acrylic copolymer for a reflective film.
Background
The reflective film can generate strong reflective effect under the irradiation of a certain light source, and provides the most effective and reliable safety guarantee for pedestrians or night operators in darkness. The reflecting film is a film with a special structure which can reflect light back to a light source by utilizing an optical principle, and consists of a film layer with good weather resistance, a micro glass bead layer, a gathering layer, a reflecting layer, an adhesive layer and a stripping layer.
The materials suitable for making film products are various, and materials such as PVC, PP, PE, PA, PU and the like can be used as production materials of the film products. However, acrylic resin is most widely used in the field of reflective films because of its excellent transparency and uv resistance, and its advantages of light retention, weather resistance, corrosion resistance, and pollution resistance.
However, the acrylic resin in the market at present loses part of low-temperature flexibility while pursuing high chemical resistance and good tensile strength, has high brittleness in a low-temperature environment, and does not meet the product requirement of a reflective film. At present, in order to solve the problem of poor low-temperature flexibility of acrylic resin, a plurality of companies generally adopt two resins with different hardness to achieve a proper hardness-hardness balance ratio, but the preparation method is complex and the processing cost is high, and the obtained acrylic resin still has certain brittleness in a low-temperature environment, cannot achieve the expected effect and has certain limitation. The invention patent with the patent number of 'CN 201310017465.3' and the name of 'hydroxy acrylic resin for a reflective film and a preparation method thereof' discloses a hydroxy acrylic resin for a reflective film and a preparation method thereof, but does not disclose specific test results, and the published documents show that although the low glass transition temperature of the hydroxy acrylic resin ensures the low-temperature flexibility of the finished product of the acrylic resin, the hydroxy acrylic resin is easy to be anti-sticky after being made into a film coating, so the hydroxy acrylic resin is not suitable for being used as a surface layer of a reflective material. Based on the above problems, it is desired to develop an acrylic resin having excellent low-temperature flexibility, balanced weather resistance and chemical resistance, and a relatively simple manufacturing process, so as to better satisfy the use of the light reflecting material.
Disclosure of Invention
The invention provides a novel preparation method of an acrylic copolymer for a reflective film, aiming at the defects that the existing acrylic resin for the reflective film loses part of low-temperature flexibility while pursuing high chemical resistance and good tensile strength, has higher brittleness in a low-temperature environment, so that the reflective film is easy to crack when being used for stamping in a low-temperature environment in winter, and the low glass transition temperature ensures the low-temperature flexibility of an acrylic resin finished product, but the anti-sticking phenomenon is easy to occur after a film coating is prepared, the acrylic resin is not suitable for being used as a surface layer of a reflective material, and the like.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a preparation method of an acrylic copolymer for a reflective film comprises the following steps of preparing a composition according to the weight ratio:
5 to 25% of a soft monomer,
10 to 35 parts of a hard monomer,
0.5 to 15 parts of functional monomer,
1.5 to 12 parts of long carbon chain monomer,
0.05 to 3 parts of an initiator,
50-80 parts of a solvent;
the soft monomer is a mixture formed by any one or more than any two of ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and n-octyl methacrylate, the hard monomer is a mixture formed by any one or more than any two of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, styrene and acrylonitrile, the long carbon chain monomer is a mixture formed by any one or more than any two of tridecyl methacrylate, octadecyl methacrylate and lauryl methacrylate, the functional monomer is a mixture formed by any one or more of a hydroxyl-containing monomer, a carboxyl-containing monomer, an amino-containing monomer and an epoxy-containing monomer, the initiator is an azo initiator or a peroxide initiator, and the solvent is a mixture formed by any one or more of acetone, ethylene glycol butyl ether, ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, isopropanol, cyclohexanone and ethylene glycol ethyl ether acetate;
the materials are selected as the components of the soft monomer for improving the flexibility of the product, promoting film formation and simultaneously ensuring that the finally prepared acrylic copolymer has certain gloss retention and color retention. The material is selected as the hard monomer component because of the side methyl group, and has higher glass transition temperature, thereby greatly improving the hydrolysis resistance and the balance of strength and elongation of the finally prepared acrylic copolymer. The materials are selected as the components of the functional monomer in order to improve the decorative property of the finally prepared acrylic copolymer to the pigment and filler and provide crosslinking sites, so that the product is crosslinked into a net structure, and the chemical resistance and the weather resistance of the product are greatly improved. The material is selected as the composition of the long carbon chain monomer, so that the content of ester groups in the copolymer is reduced, the polar solvent resistance of the finally prepared acrylic copolymer is improved, and particularly, the alcohol resistance of the product can be greatly improved. The azo or peroxide initiator is more suitable for the solution polymerization mode and the solvent system, and the acrylic copolymer prepared after the reaction has narrower molecular weight distribution, so that the processability and the comprehensive performance of the product are improved.
The preparation steps are as follows:
(1) at room temperature, weighing 45% of the total weight of the soft monomer, 16.5% of the total weight of the hard monomer, 30% of the total weight of the functional monomer, 35% of the total weight of the long carbon chain monomer, 16% of the total weight of the initiator and 15% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture A;
(2) weighing the uniformly mixed mixture A in the step (1), putting the mixture A into a reaction container provided with a stirrer, a heater, a condenser, a dropping funnel and a nitrogen inlet pipe, and opening the stirrer to stir the mixture A for 10-30 minutes;
(3) continuously inputting nitrogen into the reaction container for 10-30 minutes through a nitrogen inlet pipe;
(4) stopping inputting nitrogen, starting a heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 30-60 min when the temperature in the reaction container is increased to 75-85 ℃;
(5) weighing 55% of the total weight of the soft monomer, 83.5% of the total weight of the hard monomer, 70% of the total weight of the functional monomer, 65% of the total weight of the long carbon chain monomer, 32.5% of the total weight of the initiator and 5% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture B;
(6) uniformly and stably dripping all the mixture B uniformly mixed in the step (5) into a reaction container through a dropping funnel within 80-120 min, and keeping the temperature in the reaction container for 60-90 min after dripping;
(7) weighing 51.5 percent of the total weight of the initiator and 10 percent of the total weight of the solvent to form a mixture C, uniformly and stably dripping the mixture C into a reaction container through a dropping funnel within 60-90 min, and keeping the temperature in the reaction container for 90-210 min after dripping;
(8) weighing 70% of the total weight of the solvent, putting the solvent into a reaction container, reacting for more than 0min and less than or equal to 30min, then reducing the temperature in the reaction container, stopping the machine when the temperature in the reaction container is reduced to 40 ℃, and pouring out the solvent to obtain the acrylic copolymer.
In the step (1), according to the copolymerization activity and the competitive polymerization rate of each monomer in the reaction, better reactivity can be obtained by comparing the mixture ratio of each reaction monomer through experiments. In the step (2), the stirring time is selected to enable all reaction monomers, the solvent and the initiator to be fully mixed, so that the reaction rate is improved. In the step (3), the nitrogen is continuously input into the reaction vessel to ensure that the air in the reaction kettle is completely removed, so that the inhibition effect of oxygen in the air on the reaction is reduced. The step (4) is to pre-react a part of monomers in the reaction kettle, so that the whole reaction can be carried out stably, and the phenomenon of implosion caused by excessive heat release is avoided. In the step (5), the proportion is selected to enable each reaction monomer to better carry out copolymerization reaction, and the copolymer with narrow molecular weight distribution is more favorably obtained. The molecular weight of the prepared acrylic copolymer can be further increased after the reaction in the step (6), and the smooth proceeding of the reaction can be effectively ensured. The step (7) is provided for further supplementing the initiator and the solvent, so that the reaction conversion rate is further improved.
The acrylic copolymer prepared by the steps has stronger chemical resistance and good tensile strength, and the low-temperature flexibility is greatly improved compared with that of the common acrylic copolymer, so that the acrylic copolymer is not easy to become brittle in a low-temperature environment. Meanwhile, the anti-sticking phenomenon is not easy to occur after the film coating is prepared, so the film coating is very suitable for being used as a surface layer of a reflecting material, and the manufacturing process is simple, thereby the film coating is very in line with the requirements of the modern reflecting field.
Preferably, the preparation method of the acrylic copolymer for the reflective film comprises the following steps:
5 to 12 parts of a soft monomer,
10 to 25 parts of a hard monomer,
2 to 10 parts of functional monomer,
2 to 8 of long carbon chain monomers,
0.1 to 1 part of an initiator,
60-70 parts of a solvent;
the initiator is any one or a mixture formed by combining more than two of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl and dicumyl peroxide.
The weight ratio of the soft monomer is set in the range, so that the film forming property and the low-temperature flexibility of the product can be guaranteed, the product cannot be brittle in a low temperature environment in winter, and is not easy to crack when being used by a client in a stamping mode, and the use limitation of the acrylic resin used in the market at a low temperature can be better improved. The weight ratio of the hard monomer is set in the range, which is favorable for improving the balance of the strength and the elongation of the product, and the hard monomer added in the weight ratio range is also favorable for avoiding the phenomenon of anti-sticking of the product, so that the product has better hydrolysis resistance. The weight ratio of the functional monomer is set within the above range in order to further improve the wettability and storage stability of the finally prepared acrylic copolymer to the pigment and filler. The reason for setting the weight ratio of the long carbon chain monomer within the above range is to further improve the polar solvent resistance of the finally obtained acrylic copolymer, and particularly, to greatly improve the alcohol resistance of the acrylic copolymer. The weight ratio of the initiator is set within the above range so that the acrylic copolymer has a more suitable weight average molecular weight and molecular weight distribution, and thus is more suitable for use in the field of a light-reflecting film. The weight ratio of the solvent is set within the above range in order to have a more appropriate solid content, so that the viscosity of the acrylic copolymer is controlled within a reasonable range, and the subsequent production and processing are facilitated. The above materials are preferably used as the initiator because side reactions generated after decomposition into active radicals are less, the molecular weight distribution of the acrylic copolymer obtained after the reaction is narrower, and the viscosity of the acrylic copolymer obtained is also lower.
Preferably, in the above method for preparing an acrylic copolymer for a light-reflecting film, the weight average molecular weight of the acrylic copolymer obtained in the step (8) is 15 to 50 ten thousand g/mol.
The weight average molecular weight of the acrylic copolymer is controlled to be more than 15 kg/mol because entanglement is more likely to occur between different molecular chains within the numerical range, thereby ensuring more excellent chemical resistance, while an excessively large weight average molecular weight of the acrylic copolymer causes an excessively high viscosity of a coating film to be produced, thereby making smooth coating difficult, and therefore, it is preferable to control the weight average molecular weight to be within 50 kg/mol.
Preferably, in the above method for preparing an acrylic copolymer for a light-reflecting film, the weight average molecular weight of the acrylic copolymer obtained in the step (8) is 20 to 40 ten thousand g/mol.
The weight average molecular weight of the acrylic copolymer is controlled within the above range in order to further improve chemical resistance of the acrylic copolymer, thereby improving the practical life of the resulting product. At the same time, acrylic copolymers within this range of values have moderate viscosities and are easier to apply.
Preferably, in the above method for preparing an acrylic copolymer for a light-reflecting film, the stirring speed of the stirrer in the step (2) is 100 rpm to 150 rpm.
In the step (2), the stirring speed of the stirrer is controlled within the above range to ensure that the soft monomer, the hard monomer, the functional monomer, the long carbon chain monomer, the initiator and the solvent can be sufficiently and uniformly mixed, thereby improving the reaction rate and the resin conversion rate.
Preferably, in the above method for preparing an acrylic copolymer for a reflective film, the molecular weight distribution index of the acrylic copolymer obtained in the step (8) is 1.5 to 5.5.
Controlling the molecular weight distribution index of the acrylic copolymer within the above range is not only beneficial to improving the physical properties of the acrylic copolymer, but also beneficial to improving the processability of the acrylic copolymer, and meets the requirements of the actual production of the reflective film.
Preferably, in the above method for preparing an acrylic copolymer for a reflective film, the molecular weight distribution index of the acrylic copolymer obtained in the step (8) is 1.5 to 2.5.
The molecular weight distribution index of the acrylic copolymer is controlled within the above range in order to further improve the physical properties of the acrylic copolymer and the processability of the acrylic copolymer.
Preferably, in the above method for preparing an acrylic copolymer for a light-reflecting film, the acrylic copolymer obtained in the step (8) has a glass transition temperature of 10 to 45 ℃.
When the glass transition temperature of the acrylic copolymer is too low, the prepared paint film becomes too soft, so that the strength of the paint film cannot be improved, meanwhile, the excessively low glass transition temperature increases the possibility of the anti-sticking phenomenon of the prepared paint film, and when the glass transition temperature of the acrylic copolymer is too high, the paint film becomes too brittle in a low-temperature environment, so that the actual use effect is influenced.
Preferably, in the above method for preparing an acrylic copolymer for a light-reflecting film, the acrylic copolymer obtained in the step (8) has a glass transition temperature of 10 to 40 ℃.
The glass transition temperature of the acrylic copolymer obtained in the step (8) is controlled within the range so as to further improve the strength of the paint film, avoid the possibility of anti-sticking phenomenon caused by over-softness of the paint film, well ensure the low-temperature flexibility of the paint film, and meet the product requirements of modern society on reflective films.
Detailed Description
The invention will now be described in further detail with reference to specific embodiments, but they are not intended to limit the invention:
example 1
A preparation method of an acrylic copolymer for a reflective film comprises the following steps of preparing a composition according to the weight ratio:
the soft single body (5) is provided with a soft single body,
the hard monomer 10 is a mixture of a hard monomer,
0.5 percent of functional monomer,
1.5 of long carbon chain monomer,
the content of the initiator is 0.05,
a solvent 50;
the soft monomer is a mixture formed by any one or more than any two of ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and n-octyl methacrylate, the hard monomer is a mixture formed by any one or more than any two of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, styrene and acrylonitrile, the long carbon chain monomer is a mixture formed by any one or more than any two of tridecyl methacrylate, octadecyl methacrylate and lauryl methacrylate, the functional monomer is a mixture formed by any one or more of a hydroxyl-containing monomer, a carboxyl-containing monomer, an amino-containing monomer and an epoxy-containing monomer, the initiator is an azo initiator or a peroxide initiator, and the solvent is a mixture formed by any one or more of acetone, ethylene glycol butyl ether, ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, isopropanol, cyclohexanone and ethylene glycol ethyl ether acetate;
the preparation steps are as follows:
(1) at room temperature, weighing 45% of the total weight of the soft monomer, 16.5% of the total weight of the hard monomer, 30% of the total weight of the functional monomer, 35% of the total weight of the long carbon chain monomer, 16% of the total weight of the initiator and 15% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture A;
(2) weighing the uniformly mixed mixture A in the step (1), putting the mixture A into a reaction container provided with a stirrer, a heater, a condenser, a dropping funnel and a nitrogen inlet pipe, and opening the stirrer to stir the mixture A for 10 minutes;
(3) continuously inputting nitrogen into the reaction vessel for 10 minutes through a nitrogen inlet pipe;
(4) stopping inputting nitrogen, starting a heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 30min when the temperature in the reaction container is increased to 75 ℃;
(5) weighing 55% of the total weight of the soft monomer, 83.5% of the total weight of the hard monomer, 70% of the total weight of the functional monomer, 65% of the total weight of the long carbon chain monomer, 32.5% of the total weight of the initiator and 5% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture B;
(6) uniformly and stably dropwise adding the uniformly mixed mixture B obtained in the step (5) into a reaction container through a dropping funnel within 80min, and keeping the temperature in the reaction container for 60min after the dropwise adding is finished;
(7) weighing 51.5% of the total weight of the initiator and 10% of the total weight of the solvent to form a mixture C, uniformly and stably dropwise adding the mixture C into a reaction container through a dropping funnel within 60min, and keeping the temperature in the reaction container for 90min after dropwise adding;
(8) weighing 70% of the total weight of the solvent, putting the solvent into a reaction vessel for reaction for 30s, then reducing the temperature in the reaction vessel, stopping the reaction vessel when the temperature in the reaction vessel is reduced to 40 ℃, and pouring out the solvent to obtain the acrylic copolymer.
Preferably, the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl carbonate and dicumyl peroxide or a mixture formed by combining any two or more of the above.
Preferably, the weight average molecular weight of the acrylic copolymer obtained in the step (8) is 15 ten thousand g/mol.
Preferably, the stirring speed of the stirrer in the step (2) is 100 rpm.
Preferably, the acrylic copolymer obtained in the step (8) has a molecular weight distribution index of 1.5.
Preferably, the acrylic copolymer obtained in the step (8) has a glass transition temperature of 10 ℃.
Example 2
A preparation method of an acrylic copolymer for a reflective film comprises the following steps of preparing a composition according to the weight ratio:
the soft monomer (25) is a soft monomer,
the hard monomer (35) is a monomer,
the functional monomer (15) is a monomer,
the long carbon chain monomer 12 is a long carbon chain monomer,
an initiator (3) which is a mixture of,
a solvent 80;
the soft monomer is a mixture formed by any one or more than any two of ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and n-octyl methacrylate, the hard monomer is a mixture formed by any one or more than any two of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, styrene and acrylonitrile, the long carbon chain monomer is a mixture formed by any one or more than any two of tridecyl methacrylate, octadecyl methacrylate and lauryl methacrylate, the functional monomer is a mixture formed by any one or more of a hydroxyl-containing monomer, a carboxyl-containing monomer, an amino-containing monomer and an epoxy-containing monomer, the initiator is an azo initiator or a peroxide initiator, and the solvent is a mixture formed by any one or more of acetone, ethylene glycol butyl ether, ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, isopropanol, cyclohexanone and ethylene glycol ethyl ether acetate;
the preparation steps are as follows:
(1) at room temperature, weighing 45% of the total weight of the soft monomer, 16.5% of the total weight of the hard monomer, 30% of the total weight of the functional monomer, 35% of the total weight of the long carbon chain monomer, 16% of the total weight of the initiator and 15% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture A;
(2) weighing the uniformly mixed mixture A in the step (1), putting the mixture A into a reaction container provided with a stirrer, a heater, a condenser, a dropping funnel and a nitrogen inlet pipe, and opening the stirrer to stir the mixture A for 30 minutes;
(3) continuously inputting nitrogen into the reaction vessel for 30 minutes through a nitrogen inlet pipe;
(4) stopping inputting nitrogen, starting a heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 60min when the temperature in the reaction container is increased to 85 ℃;
(5) weighing 55% of the total weight of the soft monomer, 83.5% of the total weight of the hard monomer, 70% of the total weight of the functional monomer, 65% of the total weight of the long carbon chain monomer, 32.5% of the total weight of the initiator and 5% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture B;
(6) uniformly and stably dropwise adding the uniformly mixed mixture B obtained in the step (5) into a reaction container through a dropping funnel within 120min, and keeping the temperature in the reaction container for 90min after the dropwise adding is finished;
(7) weighing 51.5% of the total weight of the initiator and 10% of the total weight of the solvent to form a mixture C, uniformly and stably dropwise adding the mixture C into a reaction container through a dropping funnel within 90min, and keeping the temperature in the reaction container for 210min after dropwise adding;
(8) weighing 70% of the total weight of the solvent, putting the solvent into a reaction container for reaction for 30min, then reducing the temperature in the reaction container, stopping the reaction when the temperature in the reaction container is reduced to 40 ℃, and pouring out the acrylic copolymer to obtain the acrylic copolymer.
Preferably, the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl carbonate and dicumyl peroxide or a mixture formed by combining any two or more of the above.
Preferably, the weight average molecular weight of the acrylic copolymer obtained in the step (8) is 50 ten thousand g/mol.
Preferably, the stirring speed of the stirrer in the step (2) is 150 rpm.
Preferably, the acrylic copolymer obtained in the step (8) has a molecular weight distribution index of 5.5.
Preferably, the acrylic copolymer obtained in the step (8) has a glass transition temperature of 45 ℃.
Example 3
A preparation method of an acrylic copolymer for a reflective film comprises the following steps of preparing a composition according to the weight ratio:
the soft single-body 15 is provided with a soft single-body,
the hard monomer(s) 22.5,
the functional monomer is 7.75 percent,
the long carbon chain monomer is 6.75,
the initiator is 1.525 of the total weight of the mixture,
a solvent 65;
the soft monomer is a mixture formed by any one or more than any two of ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and n-octyl methacrylate, the hard monomer is a mixture formed by any one or more than any two of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, styrene and acrylonitrile, the long carbon chain monomer is a mixture formed by any one or more than any two of tridecyl methacrylate, octadecyl methacrylate and lauryl methacrylate, the functional monomer is a mixture formed by any one or more of a hydroxyl-containing monomer, a carboxyl-containing monomer, an amino-containing monomer and an epoxy-containing monomer, the initiator is an azo initiator or a peroxide initiator, and the solvent is a mixture formed by any one or more of acetone, ethylene glycol butyl ether, ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, isopropanol, cyclohexanone and ethylene glycol ethyl ether acetate;
the preparation steps are as follows:
(1) at room temperature, weighing 45% of the total weight of the soft monomer, 16.5% of the total weight of the hard monomer, 30% of the total weight of the functional monomer, 35% of the total weight of the long carbon chain monomer, 16% of the total weight of the initiator and 15% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture A;
(2) weighing the uniformly mixed mixture A in the step (1), putting the mixture A into a reaction container provided with a stirrer, a heater, a condenser, a dropping funnel and a nitrogen inlet pipe, and opening the stirrer to stir the mixture A for 20 minutes;
(3) continuously inputting nitrogen into the reaction vessel for 20 minutes through a nitrogen inlet pipe;
(4) stopping inputting nitrogen, starting a heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 45min when the temperature in the reaction container is increased to 80 ℃;
(5) weighing 55% of the total weight of the soft monomer, 83.5% of the total weight of the hard monomer, 70% of the total weight of the functional monomer, 65% of the total weight of the long carbon chain monomer, 32.5% of the total weight of the initiator and 5% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture B;
(6) uniformly and stably dropwise adding the uniformly mixed mixture B obtained in the step (5) into a reaction container through a dropping funnel within 100min, and keeping the temperature in the reaction container for 75min after the dropwise adding is finished;
(7) weighing 51.5% of the total weight of the initiator and 10% of the total weight of the solvent to form a mixture C, uniformly and stably dropwise adding the mixture C into a reaction container through a dropping funnel within 75min, and keeping the temperature in the reaction container for 150min after dropwise adding;
(8) weighing 70% of the total weight of the solvent, putting the solvent into a reaction container for reaction for 15min, then reducing the temperature in the reaction container, stopping the reaction when the temperature in the reaction container is reduced to 40 ℃, and pouring out the acrylic copolymer to obtain the acrylic copolymer.
Preferably, the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl carbonate and dicumyl peroxide or a mixture formed by combining any two or more of the above.
Preferably, the weight average molecular weight of the acrylic copolymer obtained in the step (8) is 32.5 ten thousand g/mol.
Preferably, the stirring speed of the stirrer in the step (2) is 125 rpm.
Preferably, the acrylic copolymer obtained in the step (8) has a molecular weight distribution index of 3.5.
Preferably, the acrylic copolymer obtained in the step (8) has a glass transition temperature of 27.5 ℃.
Example 4
A preparation method of an acrylic copolymer for a reflective film comprises the following steps of preparing a composition according to the weight ratio:
the soft single body (5) is provided with a soft single body,
the hard monomer 10 is a mixture of a hard monomer,
the functional monomer 2 is a mixture of a functional monomer,
the long carbon chain monomer 2 is a long carbon chain monomer,
the content of the initiator is 0.1,
a solvent 60;
the soft monomer is a mixture formed by any one or more than any two of ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and n-octyl methacrylate, the hard monomer is a mixture formed by any one or more than any two of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, styrene and acrylonitrile, the long carbon chain monomer is a mixture formed by any one or more than any two of tridecyl methacrylate, octadecyl methacrylate and lauryl methacrylate, the functional monomer is a mixture formed by any one or more of a hydroxyl-containing monomer, a carboxyl-containing monomer, an amino-containing monomer and an epoxy-containing monomer, the initiator is an azo initiator or a peroxide initiator, and the solvent is a mixture formed by any one or more of acetone, ethylene glycol butyl ether, ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, isopropanol, cyclohexanone and ethylene glycol ethyl ether acetate;
the preparation steps are as follows:
(1) at room temperature, weighing 45% of the total weight of the soft monomer, 16.5% of the total weight of the hard monomer, 30% of the total weight of the functional monomer, 35% of the total weight of the long carbon chain monomer, 16% of the total weight of the initiator and 15% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture A;
(2) weighing the uniformly mixed mixture A in the step (1), putting the mixture A into a reaction container provided with a stirrer, a heater, a condenser, a dropping funnel and a nitrogen inlet pipe, and opening the stirrer to stir the mixture A for 13 minutes;
(3) continuously inputting nitrogen into the reaction vessel for 18 minutes through a nitrogen inlet pipe;
(4) stopping inputting nitrogen, starting a heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 50min when the temperature in the reaction container is increased to 80 ℃;
(5) weighing 55% of the total weight of the soft monomer, 83.5% of the total weight of the hard monomer, 70% of the total weight of the functional monomer, 65% of the total weight of the long carbon chain monomer, 32.5% of the total weight of the initiator and 5% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture B;
(6) uniformly and stably dropwise adding the uniformly mixed mixture B obtained in the step (5) into a reaction container through a dropping funnel within 95min, and keeping the temperature in the reaction container for 80min after the dropwise adding is finished;
(7) weighing 51.5% of the total weight of the initiator and 10% of the total weight of the solvent to form a mixture C, uniformly and stably dropwise adding the mixture C into a reaction container through a dropping funnel within 80min, and keeping the temperature in the reaction container for 180min after dropwise adding;
(8) weighing 70% of the total weight of the solvent, putting the solvent into a reaction container for reaction for 24min, then reducing the temperature in the reaction container, stopping the reaction when the temperature in the reaction container is reduced to 40 ℃, and pouring out the acrylic copolymer to obtain the acrylic copolymer.
Preferably, the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl carbonate and dicumyl peroxide or a mixture formed by combining any two or more of the above.
Preferably, the weight average molecular weight of the acrylic copolymer obtained in the step (8) is 20 ten thousand g/mol.
Preferably, the stirring speed of the stirrer in the step (2) is 130 rpm.
Preferably, the acrylic copolymer obtained in the step (8) has a molecular weight distribution index of 1.5.
Preferably, the acrylic copolymer obtained in the step (8) has a glass transition temperature of 10 ℃.
Example 5
A preparation method of an acrylic copolymer for a reflective film comprises the following steps of preparing a composition according to the weight ratio:
the soft single-body 12 is provided with a soft single-body,
the hard monomer 25 is a monomer for the hard monomer,
the functional monomer 10 is a mixture of a functional monomer,
the long carbon chain of the monomer 8,
an initiator 1, an initiator, a polymerization initiator,
a solvent 70;
the soft monomer is a mixture formed by any one or more than any two of ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and n-octyl methacrylate, the hard monomer is a mixture formed by any one or more than any two of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, styrene and acrylonitrile, the long carbon chain monomer is a mixture formed by any one or more than any two of tridecyl methacrylate, octadecyl methacrylate and lauryl methacrylate, the functional monomer is a mixture formed by any one or more of a hydroxyl-containing monomer, a carboxyl-containing monomer, an amino-containing monomer and an epoxy-containing monomer, the initiator is an azo initiator or a peroxide initiator, and the solvent is a mixture formed by any one or more of acetone, ethylene glycol butyl ether, ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, isopropanol, cyclohexanone and ethylene glycol ethyl ether acetate;
the preparation steps are as follows:
(1) at room temperature, weighing 45% of the total weight of the soft monomer, 16.5% of the total weight of the hard monomer, 30% of the total weight of the functional monomer, 35% of the total weight of the long carbon chain monomer, 16% of the total weight of the initiator and 15% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture A;
(2) weighing the uniformly mixed mixture A in the step (1), putting the mixture A into a reaction container provided with a stirrer, a heater, a condenser, a dropping funnel and a nitrogen inlet pipe, and opening the stirrer to stir the mixture A for 13 minutes;
(3) continuously inputting nitrogen into the reaction vessel for 16 minutes through a nitrogen inlet pipe;
(4) stopping inputting nitrogen, starting a heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 48min when the temperature in the reaction container is increased to 78 ℃;
(5) weighing 55% of the total weight of the soft monomer, 83.5% of the total weight of the hard monomer, 70% of the total weight of the functional monomer, 65% of the total weight of the long carbon chain monomer, 32.5% of the total weight of the initiator and 5% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture B;
(6) uniformly and stably dropwise adding the uniformly mixed mixture B obtained in the step (5) into a reaction container through a dropping funnel within 90min, and keeping the temperature in the reaction container for 85min after the dropwise adding is finished;
(7) weighing 51.5% of the total weight of the initiator and 10% of the total weight of the solvent to form a mixture C, uniformly and stably dropwise adding the mixture C into a reaction container through a dropping funnel within 65min, and keeping the temperature in the reaction container for 120min after dropwise adding;
(8) weighing 70% of the total weight of the solvent, putting the solvent into a reaction container for reaction for 12min, then reducing the temperature in the reaction container, stopping the reaction when the temperature in the reaction container is reduced to 40 ℃, and pouring out the acrylic copolymer.
Preferably, the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl carbonate and dicumyl peroxide or a mixture formed by combining any two or more of the above.
Preferably, the weight average molecular weight of the acrylic copolymer obtained in the step (8) is 40 ten thousand g/mol.
Preferably, the stirring speed of the stirrer in the step (2) is 128 revolutions per minute.
Preferably, the acrylic copolymer obtained in the step (8) has a molecular weight distribution index of 2.5.
Preferably, the acrylic copolymer obtained in the step (8) has a glass transition temperature of 40 ℃.
Example 6
A preparation method of an acrylic copolymer for a reflective film comprises the following steps of preparing a composition according to the weight ratio:
the soft monomer is 8.5 percent of the soft monomer,
the hard monomer is 17.5, and the hard monomer,
the functional monomer 6 is a monomer having a functional group,
the long carbon chain monomer 5 is used as a monomer,
the content of the initiator is 0.55,
a solvent 65;
the soft monomer is a mixture formed by any one or more than any two of ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and n-octyl methacrylate, the hard monomer is a mixture formed by any one or more than any two of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, styrene and acrylonitrile, the long carbon chain monomer is a mixture formed by any one or more than any two of tridecyl methacrylate, octadecyl methacrylate and lauryl methacrylate, the functional monomer is a mixture formed by any one or more of a hydroxyl-containing monomer, a carboxyl-containing monomer, an amino-containing monomer and an epoxy-containing monomer, the initiator is an azo initiator or a peroxide initiator, and the solvent is a mixture formed by any one or more of acetone, ethylene glycol butyl ether, ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, isopropanol, cyclohexanone and ethylene glycol ethyl ether acetate;
the preparation steps are as follows:
(1) at room temperature, weighing 45% of the total weight of the soft monomer, 16.5% of the total weight of the hard monomer, 30% of the total weight of the functional monomer, 35% of the total weight of the long carbon chain monomer, 16% of the total weight of the initiator and 15% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture A;
(2) weighing the uniformly mixed mixture A in the step (1), putting the mixture A into a reaction container provided with a stirrer, a heater, a condenser, a dropping funnel and a nitrogen inlet pipe, and opening the stirrer to stir the mixture A for 13 minutes;
(3) continuously inputting nitrogen into the reaction vessel for 16 minutes through a nitrogen inlet pipe;
(4) stopping inputting nitrogen, starting a heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 48min when the temperature in the reaction container is increased to 78 ℃;
(5) weighing 55% of the total weight of the soft monomer, 83.5% of the total weight of the hard monomer, 70% of the total weight of the functional monomer, 65% of the total weight of the long carbon chain monomer, 32.5% of the total weight of the initiator and 5% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture B;
(6) uniformly and stably dropwise adding the uniformly mixed mixture B obtained in the step (5) into a reaction container through a dropping funnel within 90min, and keeping the temperature in the reaction container for 85min after the dropwise adding is finished;
(7) weighing 51.5% of the total weight of the initiator and 10% of the total weight of the solvent to form a mixture C, uniformly and stably dropwise adding the mixture C into a reaction container through a dropping funnel within 65min, and keeping the temperature in the reaction container for 120min after dropwise adding;
(8) weighing 70% of the total weight of the solvent, putting the solvent into a reaction container for reaction for 12min, then reducing the temperature in the reaction container, stopping the reaction when the temperature in the reaction container is reduced to 40 ℃, and pouring out the acrylic copolymer.
Preferably, the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl carbonate and dicumyl peroxide or a mixture formed by combining any two or more of the above.
Preferably, the weight average molecular weight of the acrylic copolymer obtained in the step (8) is 30 ten thousand g/mol.
Preferably, the stirring speed of the stirrer in the step (2) is 128 revolutions per minute.
Preferably, the acrylic copolymer obtained in the step (8) has a molecular weight distribution index of 2.
Preferably, the acrylic copolymer obtained in the step (8) has a glass transition temperature of 25 ℃.
In summary, the above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the present invention.
Claims (1)
1. A preparation method of acrylic copolymer for a reflective film is characterized by comprising the following steps: the weight average molecular weight of the acrylic copolymer is 30-40 ten thousand g/mol, the molecular weight distribution index is 2-2.5, the glass transition temperature is 25-40 ℃, and the acrylic copolymer is prepared from the following compositions in parts by weight:
5 to 12 parts of a soft monomer,
10 to 25 parts of a hard monomer,
2 to 10 parts of functional monomer,
2 to 8 of long carbon chain monomers,
0.1 to 1 part of an initiator,
60-70 parts of a solvent;
the soft monomer is a mixture formed by any one or more than any two of ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and n-octyl methacrylate, the hard monomer is a mixture formed by any one or more than any two of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, styrene and acrylonitrile, the long carbon chain monomer is a mixture formed by any one or more than any two of tridecyl methacrylate, octadecyl methacrylate and lauryl methacrylate, the functional monomer is a mixture formed by any one or more of a hydroxyl-containing monomer, a carboxyl-containing monomer, an amino-containing monomer and an epoxy-containing monomer, the solvent is a mixture formed by any one or more of acetone, ethylene glycol butyl ether, ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, isopropanol, cyclohexanone and ethylene glycol ethyl ether acetate, and the initiator is any one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxy benzoate, tert-butyl peroxy-2-ethylhexyl and dicumyl peroxide;
the preparation steps are as follows:
(1) at room temperature, weighing 45% of the total weight of the soft monomer, 16.5% of the total weight of the hard monomer, 30% of the total weight of the functional monomer, 35% of the total weight of the long carbon chain monomer, 16% of the total weight of the initiator and 15% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture A;
(2) weighing the uniformly mixed mixture A in the step (1), putting the mixture A into a reaction container provided with a stirrer, a heater, a condenser, a dropping funnel and a nitrogen inlet pipe, opening the stirrer to stir the mixture A for 10-30 minutes, wherein the stirring speed of the stirrer is 100-150 r/min;
(3) continuously inputting nitrogen into the reaction container for 10-30 minutes through a nitrogen inlet pipe;
(4) stopping inputting nitrogen, starting a heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 30-60 min when the temperature in the reaction container is increased to 75-85 ℃;
(5) weighing 55% of the total weight of the soft monomer, 83.5% of the total weight of the hard monomer, 70% of the total weight of the functional monomer, 65% of the total weight of the long carbon chain monomer, 32.5% of the total weight of the initiator and 5% of the total weight of the solvent, and mixing according to the weight ratio to prepare a mixture B;
(6) uniformly and stably dripping all the mixture B uniformly mixed in the step (5) into a reaction container through a dropping funnel within 80-120 min, and keeping the temperature in the reaction container for 60-90 min after dripping;
(7) weighing 51.5 percent of the total weight of the initiator and 10 percent of the total weight of the solvent to form a mixture C, uniformly and stably dripping the mixture C into a reaction container through a dropping funnel within 60-90 min, and keeping the temperature in the reaction container for 90-210 min after dripping;
(8) weighing 70% of the total weight of the solvent, putting the solvent into a reaction container, reacting for more than 0min and less than or equal to 30min, then reducing the temperature in the reaction container, stopping the machine when the temperature in the reaction container is reduced to 40 ℃, and pouring out the solvent to obtain the acrylic copolymer.
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