CN1155551A - Synthetic hindered amine and preparation and usage thereof - Google Patents
Synthetic hindered amine and preparation and usage thereof Download PDFInfo
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- CN1155551A CN1155551A CN 96100809 CN96100809A CN1155551A CN 1155551 A CN1155551 A CN 1155551A CN 96100809 CN96100809 CN 96100809 CN 96100809 A CN96100809 A CN 96100809A CN 1155551 A CN1155551 A CN 1155551A
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- hindered amine
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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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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Abstract
A polymeric hindered amine as optical stabilizer used in production of high-molecular film or fibre has a formula: (M1)L-(M2)Y-(I)2, where Mi is monomer, M2 is comonomer, I is initiator and Z/L+Y=0.06-0.60, and is prepared through suchs teps as dissolving M1 or M1 and M2 along with initiator in solvent, polymerizing (or copolymerizing) in inertial gas or ambient atmosphere, water precipitating or steam distillating to separate polymer from solvent, and vacuum drying.
Description
The present invention relates to a kind of polymerized hindered amine light stabilizer and preparation method thereof.
Photostabilizer is an additive indispensable in the synthetic materials, the polymer communication, and 1981,1,37, having reported with the sherwood oil is solvent, carries out precipitation polymerization and prepares hindered amine as light stabilizer.This method can only prepare molecular weight Mn＞10
4Hindered amine as light stabilizer, and molecular weight Mn is greater than 10
4The time hindered amine as light stabilizer and the consistency between the polymer poor, for example had this hindered amine as light stabilizer to produce frosting phenomenon in the fiber, the glossiness and the color of the fiber of band look are all descended to some extent.This hindered amine as light stabilizer has been arranged in the film, and transparence descends to some extent, and photo-stability efficiency is poor simultaneously.
US 4,404, and 301 have reported solution polymerization process, and the aromatic solvent that this method adopts has toxicity and polymerization velocity is slow, and heat-up time is long, make the hindered amine as light stabilizer variable color of gained rotten.
Though the Gw-540 photostabilizer good light stability of using on the domestic market has toxicity
The objective of the invention is to overcome precipitation polymerization method, to prepare photostabilizer gained molecular weight too big and make the shortcoming of using noxious solvent between itself and the polymer in the consistency difference and solution polymerization, thereby provide a kind of nontoxic polymerized hindered amine light stabilizer, itself and polymer-polymer miscibility is good and be difficult for to run off, and excellent photo-stability efficiency is arranged.This usefulness reaches the ratio of each chain link in the molecule from its suitable molecular weight.Another object of the present invention provides the preparation method of this class photostabilizer of preparation.
The general formula of polymerized hindered amine of the present invention is:
(M
1)
L-(M
2)
Y-[I]
ZM wherein
1Be the vinyl compound that contains a hindered piperidine group, its general formula is:
M, n are alternately to be 0 or 1 number, X be oxygen or-NR-, work as m=o, during n=1, when X was oxygen, general formula was represented ester, X for-NR-for the moment then general formula be acid amides; Work as m=1, during n=0, when X was oxygen, general formula was represented ether; X is-during NR-, general formula is an amine.M
2General formula be RC (R)=C (R) C (O) C (R) (R) (a), RC (R)=C (R) OR (b), RC (R)=C (R) C (O)-N (R) is (C) (R), RC (R)=C (R) C (O) OR (d), RC (R)=C (R) is (e) (R), or RC (R)=C (R)-CN (f). and the R in the general formula is selected from hydrogen, alkyl, the alkane alkyl, cyclophane base, aryl, aralkyl, heterocyclic radical, and any two or more group, wherein each group can be a 0-12 carbon atom.I in the general formula is an initiator; L is a monomer M in the polymerized hindered amine general formula
1Chain number; Y is common monomer M
2Chain number, when Y=0, photostabilizer is a kind of homopolymer; Y ≠ 0 o'clock, photostabilizer is a kind of multipolymer.Z is the fragment number of initiator, and it is the terminal group of polymkeric substance or multipolymer, and its value is 1 or 2.
Z/ (L+Y) in the photostabilizer general formula of the present invention is 0.06-0.60.
Polymerized hindered amine of the present invention is to adopt the solution polymerization process preparation: with monomer M
1Or monomer M
1With common monomer M
2, with the initiator solvent miscible after, in temperature 50-90 ℃ polymerization, polymerization time is 3-9 hour; Under inert atmosphere or ambiance, carry out polymerization or copolymerization, after polymerization finishes, go out solvent and isolate polymkeric substance, vacuum-drying and make polymerized hindered amine light stabilizer with water precipitation or wet distillation.M
1Include but not limited to methacrylic acid-2,2,6,6-tetramethyl--4-piperidines ester, methacryloyl-2,2,6,6-tetramethyl--4-piperylhydrazine, propenyl-2,2,6,6-tetramethyl--4-piperidyl ethers, or propenyl-2,2,6,6-tetramethyl--4-piperylhydrazine.M
2Include, but not limited to vinylbenzene, methacrylic ester, vinyl acetate, ketene, Vinyl Ether, vinylpyridine, (methyl) propylene piperazine, (methyl) acryloyl morpholine.Use M
1The hindered amine as light stabilizer that homopolymerization makes can be used for coating etc.; If M
1With M
2Copolymerization, M
1: M
2(molar percentage) is 95-30: 5-70; Preferred 90-50: 10-50; Best preferred 85-60: the multipolymer of 15-40 system can be used for film, fiber, engineering plastics.Used radical polymerization initiator is a superoxide, as dilauroyl peroxide etc., or azo-compound, and as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc. a kind of, or two kinds and two or more aggregations.Initiator amount is the 3-30% of monomer molar percentage ratio, is preferably 6-25%, and the best is 10-20%.Solvent for use is the saturated straight chain hydrocarbon, cyclic hydrocarbon, as No. 120 non-polar solvents such as gasoline, and acetone, methyl alcohol, ethanol isopolarity solvent, with and two or more solvent that can dissolve each other.Normally one restrain monomer 2-3 milliliter solvent.
The molecular weight of polymerized hindered amine light stabilizer of the present invention is 10
3～6 * 10
3,, when using as photostabilizer in the polypropylene film, select for use molecular weight 1 * 10 at the processing polyethylene
3～4 * 10
3, be preferably 1 * 10
3～2 * 10
3, this class polymerized hindered amine is dissolved in benzene, organic solvents such as alcohol, ketone, ether, ester.
Polymerized hindered amine light stability factor of the present invention is 3.7 times of commodity photostabilizer PDS, and is good and have an excellent photo-stability efficiency with polymer-polymer miscibility.
Embodiment 1, with 0.0300 mole of (promptly 6.7600 gram) methacrylic acid-2,2,6,6-tetramethyl--4-piperidines ester (TMPM), 0.0036 mole of (i.e. 0.5920 gram) Diisopropyl azodicarboxylate (AIBN) adds 20.3 milliliters of acetone and adds in the polymerization bottle, stirring and dissolving, 56 ℃ of polymerizations 8 hours, carry out drying after steaming solvent with water precipitation or water vapor, make polymerized hindered amine, polymer yield is 95.6%, nitrogen content 6.67%, melt temperature are 136-163 ℃, and 200 ℃ of following thermal weight losses are 2.0%; 275 ℃ of following thermal weight losses are 12.0%, number-average molecular weight 2.54 * 10
3, this class TMPM homopolymer can be used for coating etc.
Implement 2, with 0.0150 mole of TMPM, 0.0150 in mole vinylbenzene and 0.0054 mole (i.e. 0.8867 gram) 11.5 milliliters of ethanol of Diisopropyl azodicarboxylate (AIBN) adding, stirring and dissolving is at 75 ℃ of polymerase 17s hour, use water precipitation, make polymerized hindered amine after the drying, its yield is 109%, nitrogen content 5.97%, melt temperature is 104-113 ℃, 200 ℃ of following thermal weight losses are that 1.5%, 275 ℃ of following thermal weight loss is 6.0%, and number-average molecular weight is 2.11 * 10
3
Embodiment 3, replace ethanol among the embodiment 2 with methyl alcohol, carry out the copolymerization identical at 64 ℃ with embodiment 2, the hindered amine of the aggretion type that makes, its yield is 102%, nitrogen content is 6.16%, and melt temperature is 92-102 ℃, and 200 ℃ of following thermal weight losses are 3.0%, 275 ℃ of following thermal weight losses are 10%, and number-average molecular weight is 1.58 * 10
3
Embodiment 4, replace ethanol among the embodiment 2 with acetone, carry out the copolymerization identical at 56 ℃ with embodiment 2, make polymerized hindered amine, its yield is 104%, nitrogen content is 6.22% melt temperature 99-113 ℃, 200 ℃ of following thermal weight losses are that 2.0%, 275 ℃ of following thermal weight loss is 7.0%, and number-average molecular weight is 1.53 * 10
3
The hindered amine that 0.1000 gram embodiment 4 is made is dissolved in methylene dichloride, adds 100 gram polypropylene powders, and 180 ℃ are pressed into 100 ± 5 μ films, carry out artificial accelerated light ageing, are that 0.05 o'clock time corresponding is photoxidation inductive phase with the carbonyl absorption increment.Be 138.5 hours its inductive phase.Be 24 hours polypropylene screen photoxidation inductive phase that does not add stablizer.Be 113.5 hours inductive phase that adds the polypropylene screen of commodity photostabilizer Chimassorb 944.Be 38 hours inductive phase that adds the polypropylene screen of commodity photostabilizer PDS.
Embodiment 5, with 0.0600 mole of TMPM, 0.0100 mole of vinylbenzene, 0.0126 mole of AIBN add in 46.0 milliliters of acetone, stirring and dissolving at 57 ℃ of polymerase 17s hour, is used water precipitation, dry, make polymerized hindered amine, yield 97%, nitrogen content 6.97, melt temperature is 125-135 ℃, 200 ℃ of following thermal weight losses are that 4.0%, 275 ℃ of following thermal weight loss is 8.0%, and number-average molecular weight is 1.70 * 10
3
This polymerized hindered amine, its condition is with embodiment 4 when carrying out artificial accelerated light ageing, and its photoxidation inductive phase is 138.5 hours; Carried out atmospheric aging, through 13 months tan by the sun, had 3 to be complete in 10 sample films, 2 is incomplete, and adds the film of Chimassorb944, all pulverizes.
With the hindered amine of embodiment 5 preparations, add in the polyethylene, its add-on is 0.30%, and film is carried out atmospheric exposure, the tensile strength of surveying the reservation of solarization caudacoria is for shining preceding 50% pairing time (T
50).The polyethylene film T that contains hindered amine of the present invention
50Be 21 months, and contain the T of the film of Chimassorb944
50It is 19 months.The T that contains the film of GW-540
50It is 18 months.
Embodiment 6, with 0.0150 mole of TMPM, 0.0150 mole vinylbenzene and 0.0054 mole of AIBN add in 11.5 milliliters of acetone, stirring and dissolving 56 ℃ of polymerizations 4 hours, is used water precipitation, make polymerized hindered amine after the drying, its yield is 94.0%, and nitrogen content is 6.06%, and melt temperature is 96-106 ℃, 200 ℃ of following thermal weight losses are that 3.0%, 275 ℃ of following thermal weight loss is 11%.Number-average molecular weight is 1.25 * 10
3
Embodiment 7, with 0.1000 mole of TMPM, 0.0300 mole of vinylbenzene, 0.0234 mole of AIBN and 130 milliliters of No. 120 gasoline add in the polymerization bottle, stirring and dissolving after 6 hours, is removed gasoline with steam distillation in 72 ℃ of polymerizations.Get aggretion type amine resistance amine behind the desciccate, yield 97.6%, nitrogen content 6.42%, melt temperature are 124-132 ℃; 200 ℃ of following thermal weight losses are that 1.0%, 275 ℃ of following thermal weight loss is 5.0%, and number-average molecular weight is 1.78 * 10
3
Claims (10)
1, a kind of polymerized hindered amine is the vinyl polymer that contains the hindered piperidine group, it is characterized in that described polymerized hindered amine general formula is:
(M
1)
L-(M
2)
Y-[I]
ZDescribed monomer M
1General formula is
M=0, n=1, when X was oxygen, general formula was an ester, described monomer M
2General formula be RC (R)=C (R) (R), described I is an initiator, described L is a monomer M
1Chain number; Y is common monomer M
2Chain number, Z is the fragment number of initiator, described R is a hydrogen, alkyl, the alkane alkyl, the cyclophane base, aryl, aralkyl, heterocyclic radical, and any two or more group, wherein each group can be a 0-12 carbon atom.
2, a kind of polymerized hindered amine according to claim 1 is characterized in that described Z/ (L+Y) is 0.06-0.60.
3, a kind of method for making of polymerized hindered amine is characterized in that adopting solution polymerization process, with monomer M
1Or monomer M
1With common monomer M
2Add initiator with the miscible back of solvent, polymerization temperature is 50-90 ℃, polymerization time 3-9 hour, under inert atmosphere or ambiance, carry out polymerization or copolymerization, after polymerization finishes, go out solvent and isolate polymkeric substance, vacuum-drying and make polymerized hindered amine with water precipitation or wet distillation.
4, a kind of polymerized hindered amine according to claim 1 is characterized in that described M
1Be methacrylic acid-2,2,6,6-tetramethyl--4-piperidines ester.
5, a kind of polymerized hindered amine according to claim 1 is characterized in that described M
2Be vinylbenzene.
6, a kind of polymerized hindered amine according to claim 1 is characterized in that described initiator is a Diisopropyl azodicarboxylate.
7, a kind of polymerized hindered amine method for making according to claim 3 is characterized in that described M
1: M
2(molar percentage) is 95-30: 5-70.
8, a kind of polymerized hindered amine method for making according to claim 3 is characterized in that Diisopropyl azodicarboxylate: (methacrylic acid-2,2,6,6-tetramethyl--4-piperidines ester and vinylbenzene)=and be 3-30% in molar ratio.
9, a kind of polymerized hindered amine method for making according to claim 3 is characterized in that described solvent is gasoline or acetone, methyl alcohol, ethanol or its two or more solvent that can dissolve each other.
10, the purposes of a kind of polymerized hindered amine according to claim 1 is characterized in that the photostabilizer as preparation polyethylene, polypropylene film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96100809 CN1155551A (en) | 1996-01-22 | 1996-01-22 | Synthetic hindered amine and preparation and usage thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96100809 CN1155551A (en) | 1996-01-22 | 1996-01-22 | Synthetic hindered amine and preparation and usage thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1155551A true CN1155551A (en) | 1997-07-30 |
Family
ID=5116758
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|---|---|---|---|
| CN 96100809 Pending CN1155551A (en) | 1996-01-22 | 1996-01-22 | Synthetic hindered amine and preparation and usage thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374173A (en) * | 2013-07-31 | 2013-10-30 | 兰州金土地塑料制品有限公司 | Durable mulching film |
| CN104371053A (en) * | 2014-09-11 | 2015-02-25 | 四川大学 | Hindered amine light stabilizer with characteristics of high molecular weight and narrow molecular weight distribution, and preparation method thereof |
| CN104822714A (en) * | 2012-12-07 | 2015-08-05 | 日本曹达株式会社 | Method for producing polymer |
| CN111808225A (en) * | 2020-06-22 | 2020-10-23 | 宿迁联盛科技股份有限公司 | High molecular weight polymeric light stabilizer and preparation method thereof |
| CN114195921A (en) * | 2021-12-13 | 2022-03-18 | 天集化工助剂（沧州）有限公司 | Polymeric steric hindrance amine and preparation method and application thereof |
-
1996
- 1996-01-22 CN CN 96100809 patent/CN1155551A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104822714A (en) * | 2012-12-07 | 2015-08-05 | 日本曹达株式会社 | Method for producing polymer |
| CN104822714B (en) * | 2012-12-07 | 2017-10-13 | 日本曹达株式会社 | The manufacture method of polymer |
| CN103374173A (en) * | 2013-07-31 | 2013-10-30 | 兰州金土地塑料制品有限公司 | Durable mulching film |
| CN103374173B (en) * | 2013-07-31 | 2015-10-21 | 兰州金土地塑料制品有限公司 | Durable type mulch film |
| CN104371053A (en) * | 2014-09-11 | 2015-02-25 | 四川大学 | Hindered amine light stabilizer with characteristics of high molecular weight and narrow molecular weight distribution, and preparation method thereof |
| CN111808225A (en) * | 2020-06-22 | 2020-10-23 | 宿迁联盛科技股份有限公司 | High molecular weight polymeric light stabilizer and preparation method thereof |
| CN111808225B (en) * | 2020-06-22 | 2023-01-20 | 宿迁联盛科技股份有限公司 | High molecular weight polymeric light stabilizer and preparation method thereof |
| CN114195921A (en) * | 2021-12-13 | 2022-03-18 | 天集化工助剂（沧州）有限公司 | Polymeric steric hindrance amine and preparation method and application thereof |
| CN114195921B (en) * | 2021-12-13 | 2024-06-11 | 天集化工助剂（沧州）有限公司 | Polymeric sterically hindered amine and preparation method and application thereof |
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