CN111808225B - High molecular weight polymeric light stabilizer and preparation method thereof - Google Patents
High molecular weight polymeric light stabilizer and preparation method thereof Download PDFInfo
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- CN111808225B CN111808225B CN202010576080.0A CN202010576080A CN111808225B CN 111808225 B CN111808225 B CN 111808225B CN 202010576080 A CN202010576080 A CN 202010576080A CN 111808225 B CN111808225 B CN 111808225B
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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Abstract
The invention belongs to the technical field of plastic additives, and particularly relates to a high molecular weight polymeric light stabilizer and a preparation method thereof, which take 2,2,6,6-tetramethyl-N- (4-vinyl phenyl) piperidine-4-amine and propylene as raw materials, carry out polymerization reaction under the action of a catalyst and under the conditions of certain temperature and pressure, after the reaction is finished, cool and wash, dehydrate and decolor by using active carbon, filter and distill filtrate to obtain the high molecular weight polymeric light stabilizer; the high molecular weight polymeric light stabilizer is an auxiliary agent which can inhibit or slow down the degradation of a high molecular material due to photo-oxidation, has excellent thermal stability and low volatility, and has better compatibility with the high molecular material; the synthesis process is simple, the preparation cost is low and the yield is high.
Description
Technical Field
The invention belongs to the technical field of plastic additives, and particularly relates to a high molecular weight polymeric light stabilizer and a preparation method thereof.
Background
The light stabilizer is an additive of high molecular products, which can shield or absorb the energy of ultraviolet rays, quench singlet oxygen and decompose hydroperoxide into inactive substances, etc., so that the possibility of photochemical reaction can be eliminated or slowed down, and the process of photoaging can be prevented or delayed under the radiation of light, thereby achieving the purpose of prolonging the service life of the high molecular products.
The hindered amine is an organic amine compound with steric hindrance, has a good inhibition effect on the photo-oxidative degradation reaction of high polymers and organic compounds, and is a light stabilizer with excellent performance. However, the molecular weight of the existing hindered amine light stabilizer is generally small, the compatibility with high molecular materials is not good, and the existing hindered amine light stabilizer is not resistant to extraction, so that the research on the high molecular weight hindered amine light stabilizer is the leading trend of the market of the existing light stabilizer.
The high molecular weight polymeric light stabilizer has the characteristics of excellent processing thermal stability, very low volatility, migration resistance, extraction resistance, gas fading resistance and the like. The light stabilizer has good resin intermiscibility and good water extraction resistance, and has excellent long-acting light aging resistance compared with a common low-molecular-weight hindered amine light stabilizer. The product is widely used for products such as polypropylene (pp), polyethylene (pe), polystyrene (ps), abs resin, polyurethane (pu), polyester elastomer and the like. Has good synergistic effect with the antioxidant and the ultraviolet absorbent, and can further improve the heat resistance and the light aging resistance of the product.
Disclosure of Invention
The invention solves the technical problems in the prior art and provides a high molecular weight polymeric light stabilizer and a preparation method thereof.
In order to solve the problems, the technical scheme of the invention is as follows:
a high molecular weight polymeric light stabilizer having the formula:
wherein n =10 to 14.
The synthetic process route of the high molecular weight polymeric light stabilizer is as follows:
wherein n =10 to 14.
Preferably, the preparation method of the high molecular weight polymeric light stabilizer comprises the following steps:
step 1, adding 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine into a polymerization reaction kettle, adding a proper amount of organic solvent, starting stirring, replacing air with nitrogen, and introducing a certain mass of propylene gas;
and 2, adding a polymerization initiator, a catalyst and a cocatalyst, increasing the pressure in the reaction kettle by nitrogen, starting a heating system, raising the temperature to carry out polymerization reaction, cooling and washing after a period of reaction, adding activated carbon into an organic layer after water separation to carry out dehydration and decoloration, filtering to remove the activated carbon, and distilling the filtrate to obtain the high-molecular-weight polymeric light stabilizer.
Preferably, the intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine, propylene, a solvent, a catalyst, a polymerization initiator, a cocatalyst and activated carbon are fed in a mass ratio of: 1.
Preferably, the organic solvent in step 1 is any one of methanol, ethanol, cyclohexane and tetrahydrofuran.
Preferably, the polymerization initiator in step 2 is any one of cumene hydroperoxide, tert-butyl hydroperoxide and di-tert-butyl peroxide, the catalyst is any one of titanocene dichloride, zirconocene dichloride and titanium chloride/aluminum alkyl, and the auxiliary catalyst is any one of MAO, EAO and modified MMAO.
Preferably, the polymerization temperature in the step 2 is 80-130 ℃, the polymerization pressure is 2.0-6.0Mpa, and the reaction time is 4-10 hours.
Preferably, the preparation method of the intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine in the step 1 comprises the following steps:
adding a certain amount of p-bromostyrene into a reaction kettle, adding a proper amount of organic solvent and polymerization inhibitor, starting stirring to uniformly mix the p-bromostyrene and the polymerization inhibitor, controlling the temperature to be 50-80 ℃, dropwise adding 4-amino-2,2,6,6-tetramethylpiperidine, controlling the temperature to be 50-80 ℃ after dropwise adding, starting dropwise adding alkali liquor, keeping the temperature to be 80-110 ℃ after dropwise adding, reacting for 3-8 hours, washing with water after the reaction is finished, taking an organic layer after water is separated, and evaporating the solvent to dryness to obtain an intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine;
preferably, the materials of the p-bromostyrene, the 4-amino-2,2,6,6-tetramethylpiperidine, the organic solvent, the polymerization inhibitor and the alkali are calculated according to the mass ratio: 1.
Compared with the prior art, the invention has the advantages that,
the high molecular weight polymeric light stabilizer obtained by the invention is an auxiliary agent which can inhibit or slow down the degradation of a high molecular material due to photo-oxidation, and compared with the prior HALS product, the high molecular weight polymeric light stabilizer has more excellent ultraviolet and thermal stability, low volatility and better compatibility with the high molecular material; has good compatibility with most industrial solvents and excellent polymer compatibility, and is suitable for polypropylene, polyethylene plastics, fiber products, rubber products and the like.
The high molecular weight polymeric light stabilizer has the advantages of simple synthesis process, low preparation cost and high yield, and is an ideal process for realizing industrial production.
The specific implementation mode is as follows:
in order to enhance the understanding of the present invention, the following detailed description is given in conjunction with examples.
Example 1:
a process for the preparation of a high molecular weight polymeric light stabilizer comprising the steps of:
adding 50.0g of an intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine into a polymerization reaction kettle, then adding 200.0g of an absolute ethyl alcohol solvent, starting stirring, replacing air with nitrogen, then introducing 9.25g of propylene gas, adding 0.1g of polymerization initiator cumene hydroperoxide, 0.25g of a catalyst titanocene dichloride and 0.1g of a cocatalyst MAO, then increasing the pressure in the reaction kettle to 2.0MPa by nitrogen, starting a heating system, raising the temperature to 80 ℃ for polymerization reaction, after 4 hours of reaction, decompressing, cooling and washing with water, after water separation, adding 0.4g of activated carbon into an organic layer for dehydration and decoloration, filtering to remove the activated carbon, and distilling a filtrate to obtain 51.5g of the high molecular weight polymerization type light stabilizer.
Example 2:
a method for preparing a high molecular weight polymeric light stabilizer, comprising the steps of:
adding 100.0g of intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine into a polymerization reaction kettle, then adding 500.0g of cyclohexane solvent, starting stirring, replacing air with nitrogen, then adding 20.0g of propylene gas, adding 0.25g of polymerization initiator tert-butyl hydroperoxide, 0.61g of catalyst titanocene dichloride and 0.25g of cocatalyst MAO, then increasing the pressure in the reaction kettle to 2.5Mpa by nitrogen, starting a heating system, increasing the temperature to 90 ℃ for polymerization reaction, after 5 hours of reaction, decompressing, cooling and washing, after water separation, adding 0.8g of activated carbon into an organic layer for dehydration, filtering and removing the activated carbon, and distilling the filtrate to obtain 108.5g of the high molecular weight polymerization type light stabilizer.
Example 3:
a method for preparing a high molecular weight polymeric light stabilizer, comprising the steps of:
adding 150.0g of intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine into a polymerization reaction kettle, then adding 750.0g of methanol solvent, starting stirring, replacing air with nitrogen, then introducing 30.5g of propylene gas, adding 0.45g of polymerization initiator tert-butyl hydroperoxide, 1.5g of catalyst titanocene dichloride and 0.45g of cocatalyst MAO, then increasing the pressure in the reaction kettle to 3.5Mpa with nitrogen, starting a heating system, raising the temperature to 95 ℃ for polymerization reaction, after 6 hours of reaction, decompressing, cooling and washing with water, after water separation, adding 1.5g of active carbon into an organic layer for dehydration and decoloration, filtering to remove the active carbon, and distilling the filtrate to obtain 162.1g of the high molecular weight polymerization type light stabilizer.
Example 4:
a method for preparing a high molecular weight polymeric light stabilizer, comprising the steps of:
adding 200.0g of an intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine into a polymerization reaction kettle, then adding 1100.0g of a methanol solvent, starting stirring, replacing air with nitrogen, then introducing 43.0g of propylene gas, adding 0.7g of polymerization initiator tert-butyl hydroperoxide, 2.2g of a catalyst zirconocene dichloride and 0.7g of a cocatalyst MAO, then increasing the pressure in the reaction kettle to 4.0MPa with nitrogen, starting a heating system, raising the temperature to 100 ℃ for polymerization reaction, after 6 hours of reaction, decompressing, cooling and washing with water, after water separation, adding 2.1g of activated carbon into an organic layer for dehydration and decoloration, filtering to remove the activated carbon, and distilling a filtrate to obtain 218.1g of the high molecular weight polymerization type light stabilizer.
Example 5:
a method for preparing a high molecular weight polymeric light stabilizer, comprising the steps of:
230.0g of intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine is added into a polymerization reaction kettle, 1800.0g of methanol solvent is added, stirring is started, air is replaced by nitrogen, 43.0g of propylene gas is introduced, 0.85g of polymerization initiator di-tert-butyl peroxide, 2.56g of catalyst zirconocene dichloride and 0.85g of cocatalyst EAO are added, the pressure in the reaction kettle is increased to 5.0Mpa by nitrogen, a heating system is started, the temperature is increased to 110 ℃ for polymerization reaction, after 7 hours of reaction, pressure is released, water washing is carried out, 2.5g of active carbon is added into an organic layer after water separation for dehydration and decoloration, the active carbon is filtered and removed, and the filtrate is distilled to obtain 251.2g of the high molecular weight polymeric light stabilizer.
Example 6:
a process for the preparation of a high molecular weight polymeric light stabilizer comprising the steps of:
adding 300.0g of intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine into a polymerization reaction kettle, adding 3000.0g of methanol solvent, starting stirring, replacing air with nitrogen, then introducing 74.4g of propylene gas, adding 1.5g of polymerization initiator di-tert-butyl peroxide, 4.5g of catalyst titanocene dichloride and 1.5g of cocatalyst MAO, then introducing nitrogen to increase the pressure in the reaction kettle to 6.0Mpa, starting a heating system, raising the temperature to 130 ℃ for polymerization reaction, after 10 hours of reaction, releasing pressure, reducing the temperature and washing with water, after water separation, adding 3.2g of active carbon into an organic layer for dehydration and decoloration, filtering to remove the active carbon, and distilling the filtrate to obtain 346.8g of the high molecular weight polymerization type light stabilizer.
Example 7:
the samples obtained in examples 1 to 6 were subjected to thermogravimetric data, the average value thereof was taken and compared with the thermogravimetric data of some existing polymeric light stabilizers in the market, and the results are shown in the following table:
by comparison, the polymeric light stabilizer requires a higher temperature at the same 5% and 10% loss, indicating that the polymeric light stabilizer is less likely to be lost and the high temperature performance is more beneficial at the same processing temperature.
Example 8:
the stabilizer is added into a PP product according to the weight ratio of 0.1 percent and 0.5 percent respectively, and then the performances before and after the addition are respectively detected, specifically as follows:
| performance of | Non-added PP | Adding 0.1% of PP | Adding 0.5% of PP |
| Hardness, shore A/D | 64 | 71 | 76 |
| Impact strength, KJ/m 2 | 6.37 | 6.95 | 7.17 |
| Impact after aging for 400hStrength, KJ/m 2 | 3.46 | 5.75 | 6.14 |
| Impact strength after 800h ageing, KJ/m 2 | 1.30 | 3.76 | 4.18 |
| Compression set, 100 ℃ 22h | 35％ | 29％ | 25％ |
The hardness in the table is directly measured by an A-type shore durometer; the impact strength is measured by adopting a Zwick5113 intelligent digital pendulum bob impact tester, the specifications of the sample pieces are that the length of the sample is 80 +/-2 mm, the width is 10 +/-0.2 mm, the thickness is 4 +/-0.2 mm, the notch depth of the sample is 1/3 of the thickness of the sample, the notch width is 2 +/-0.2 mm, the number of each sample piece is 10, and the average value is measured to obtain the final impact strength of each sample piece; the aging equipment is a fluorescent ultraviolet lamp aging test box, and the experimental conditions are as follows: the lamp light type is UV-A, and the irradiance is 0.89W/m 2 The illumination is carried out for 8 hours at 60 ℃, the condensation is carried out for 4 hours at 50 ℃, and the aging is carried out circularly and alternately; the compression set is measured as the percentage of the original height to which the sample failed to recover, as measured by 35% compression set for the unadditized PP, which means that the sample recovered only 65% of the compressed thickness.
The detection results of the embodiment 7 and the embodiment 8 show that the product has excellent high-temperature processing resistance compared with the existing polymerization type light stabilizer product in the market, and has good dispersibility when being added into a PP material, so that the service performance of the PP material can be obviously improved.
Remarking: MAO is methylaluminoxane, EAO ethylaluminoxane and MMAO is modified methylaluminoxane.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and also comprise the technical scheme formed by equivalent replacement of the technical features. The present invention is not limited to the details given herein, but is within the ordinary knowledge of those skilled in the art.
Claims (6)
1. A high molecular weight polymeric light stabilizer, characterized in that it is prepared by a process comprising the steps of:
step 1, adding an intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine into a polymerization reaction kettle, adding a proper amount of organic solvent, starting stirring, replacing air with nitrogen, and introducing propylene gas; the intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidin-4-amine has the following structural formula:
and 2, adding a polymerization initiator, a catalyst and a cocatalyst, increasing the pressure in the reaction kettle by nitrogen, starting a heating system, raising the temperature to carry out polymerization reaction, cooling and washing after a period of reaction, adding activated carbon into an organic layer after water separation, dehydrating and decoloring, filtering to remove the activated carbon, and distilling the filtrate to obtain the high-molecular-weight polymeric light stabilizer.
2. The high molecular weight polymeric light stabilizer of claim 1 wherein intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidin-4-amine is prepared by the process of:
adding p-bromostyrene into a reaction kettle, adding a proper amount of organic solvent and polymerization inhibitor, starting stirring to uniformly mix the p-bromostyrene and the polymerization inhibitor, controlling the temperature to be 50-80 ℃, dropwise adding 4-amino-2,2,6,6-tetramethylpiperidine, controlling the temperature to be 50-80 ℃, starting dropwise adding alkali liquor, keeping the temperature to be 80-110 ℃ after dropwise adding, reacting for 3-8 hours, washing with water after the reaction is finished, taking an organic layer after water is separated, and evaporating the solvent to dryness to obtain an intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine;
the materials of the p-bromostyrene, the 4-amino-2,2,6,6-tetramethyl piperidine, the organic solvent, the polymerization inhibitor and the alkali are calculated according to the mass ratio: 1.
3. The high molecular weight polymeric light stabilizer of claim 2, wherein the intermediate 2,2,6,6-tetramethyl-N- (4-vinylphenyl) piperidin-4-amine, propylene, organic solvent, catalyst, polymerization initiator, cocatalyst and activated carbon are added by mass ratio: 1.
4. The polymeric light stabilizer of claim 2, wherein the organic solvent in step 1 is any one of methanol, ethanol, cyclohexane and tetrahydrofuran.
5. The high molecular weight polymeric light stabilizer of claim 2, wherein the polymerization initiator in step 2 is any one of cumene hydroperoxide, tert-butyl hydroperoxide and di-tert-butyl peroxide, the catalyst is any one of titanocene dichloride, zirconocene dichloride and titanium chloride/aluminum alkyl, and the auxiliary catalyst is any one of MAO, EAO and modified MMAO.
6. The polymeric light stabilizer of claim 2, wherein the polymerization temperature in step 2 is 80-130 ℃, the polymerization pressure is 2.0-6.0MPa, and the reaction time is 4-10 hours.
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| CN105601792A (en) * | 2016-01-21 | 2016-05-25 | 四川大学 | Preparation method of controllable molecular weight copolymerized hindered amine light stabilizer |
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2020
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| US5101033A (en) * | 1987-08-12 | 1992-03-31 | Atochem North America, Inc. | Process for preparing reactive hindered amine light stabilizers |
| CN1088590A (en) * | 1992-12-24 | 1994-06-29 | 中国科学院化学研究所 | A kind of method for making that is used as the multipolymer that contains the hindered amine side group of photostabilizer |
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