CN1039420C - Method for prepn. of high molecular stabilizator having self-concerted effect - Google Patents

Method for prepn. of high molecular stabilizator having self-concerted effect Download PDF

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CN1039420C
CN1039420C CN92110500A CN92110500A CN1039420C CN 1039420 C CN1039420 C CN 1039420C CN 92110500 A CN92110500 A CN 92110500A CN 92110500 A CN92110500 A CN 92110500A CN 1039420 C CN1039420 C CN 1039420C
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hbp
synergistic effect
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hindered amine
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CN1084183A (en
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吕起镐
龚建春
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Institute of Chemistry CAS
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Abstract

The present invention relates to a preparation method for high molecular light stabilizers with autosynergistic effect. Side chains of the high molecular light stabilizers simultaneously have hindered amine (HA) and o-hydroxy benzophenone (HBP) groups. The high molecular light stabilizers are made from alkene unsaturated monomers with 2, 2, 6, 6-tetramethyl piperidine (hindered amine-HA) and 2-Hydroxybenzophenone (HBP) light stability groups in a free radical polymerization method. Polymer light stability experiments prove that the high molecular light stabilizers prepared by the method of the present invention have obvious synergistic effect. The high molecular light stabilizers with the autosynergistic effect prepared by the present invention are a kind of fire-new light stability auxiliary agents.

Description

Method for prepn. of high molecular stabilizator having self-concerted effect
The novel high polymer light with auto-synergistic effect that the present invention relates to have simultaneously on a kind of side chain hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group is stablized the preparation method of chaste tree.
Hindered amine compound has been widely used in the stablizing of various synthetic polymers (U.S.P4,038,280) as the efficiency light stablizer.Recently adopt a class to have the hindered amine as light stabilizer of higher molecular weight again, thereby can obtain more satisfied light stabilising effect (U.S.P4,233,412; " polymer communication " 5,285 (1979)).Dissimilar photostabilizer mixes to use higher light stabilising effect, i.e. synergistic effect in the time of usually can obtaining to use separately respectively than them.Self does not absorb hindered amine light stabilizer) UV-light of 2900A.Therefore, they and uv-absorbing agent such as the O-hydroxyl-diphenyl ketone compounds synergistic effect of mixing when shared has been carried out developing (U.S.P4,110,304 widely; Still in work in the past, hindered amine light stabilizer and O-hydroxyl-diphenyl ketone class uv-absorbing agent all are to form the light stabilising system with form of mixtures for ApplPolym.Sci.vol.27,2761 vol. (1982).Often exist some inevitable shortcomings this moment, the molecular weight size is different with chemical property separately owing to them as (1), so they are different with consistency that is stabilized polymkeric substance and dispersive ability therein.Therefore be difficult to guarantee that they are kept evenly, the relative ratio of components of constant in polymkeric substance; (2) because their thermal characteristics differences separately so the thermosteresis in the course of processing is also different, therefore are difficult for the stable of the initial relative concentration of maintenance.Thereby make the light stabilising effect often can not reach perfect condition.
The present inventor overcomes above-mentioned shortcoming once to have reported a kind of and with the chemical bonding method HA and HBP are attached at the novel high polymer photostabilizer with auto-synergistic effect in the same molecule, (The 6thChina-Japan Symposium on RadicalPolymerization, Guilin, China October 8-12.1991 P113) the purpose of this invention is to provide above-mentioned detailed preparation method with high-molecular optical stablizer of auto-synergistic effect:
Auto-synergistic effect high-molecular optical stablizer of the present invention contains HA and two kinds of light of HBP are stablized group.They are connected in the same high-molecular optical stablizer molecule as side chain.Exactly the said auto-synergistic effect high-molecular optical of the present invention stablizer is that a kind of side chain has the multipolymer that HA and HBP light are stablized group, and such multipolymer is to make with the vinyl monomer copolymerization that has HA and HBP respectively.Can also add the 3rd monomer when carrying out copolymerization regulates prepared high-molecular optical stablizer and is stabilized consistency between the polymkeric substance.So auto-synergistic effect high-molecular optical stablizer of the present invention is to contain the copolymer that the vinyl monomer of HA and HBP makes respectively, also can be they and the 3rd certain monomer (M 3) terpolymer that makes of copolymerization, on their side chain, have the HBP substituting group of HA respectively.
The vinyl monomer that above-mentioned HA of containing or HBP light are stablized group is: R wherein 1For
Figure C9211050000033
(the R of hindered amine-HA) 2For
Figure C9211050000034
Monomer (I) is a 4-allyloxy-2,2,6,6-tetramethyl piperidine (M EHA) and monomer (II) be 4-allyloxy-2-dihydroxy benaophenonel (M EHBP) be respectively by allyl bromide 98 and 4-hydroxyl-2,2,6,6-tetramethyl piperidine and 2,4 dihydroxyl benzophenone reaction make.
Above-mentioned the 3rd monomer is α-vinyl monomer (M 3), can select according to being stabilized polymer properties, they comprise:
The acrylic or methacrylic esters of gallic acid:
Figure C9211050000035
(R wherein 3) be H, or-CH 3, R 4Alkyl for 1-18 carbon;
Vinylbenzene and derivative thereof;
Maleic anhydride, acrylamide, vinyl cyanide and vinyl acetate etc.
It is of the present invention that to have good high-molecular optical stablizer of answering from collaborative association be by M EHAAnd M EHBPAnd M 3Copolymerization makes, and the ratio of components of three kinds of vinyl monomers (weight %) is M 3: (M EHA+ M EHBP)=80-0: 20-100, but with 70-0: 30-100 is better, especially with 55: 45 the bests, wherein M EHA: M EHBP(weight %) can be 90-10: 10-90, but with 80-20: 20-80 is better, and best than being 75: 25.
The high-molecular optical stablizer of auto-synergistic effect of the present invention is by M EHA: M EHBPAnd M 3Make by free radicals copolymerization reaction, used radical copolymerization initiator is organo-peroxide one dilauroyl peroxide, also can be azo-compound such as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.The 0.2-5% that their consumption is generally the reactant gross weight is advisable with 0.5-3%, especially with 1-2% the best.
Auto-synergistic effect high-molecular optical stablizer preparation technology of the present invention is: take by weighing required monomer by described ratio of components and be dissolved in the 2-4 times of organic solvent; Add the radical copolymerization initiator, under agitation carry out polyreaction.The controlled temperature scope is 50-90 ℃, and temperature is 60-70 ℃ preferably, and the reaction times is 6-10 hour, and reaction at the end with 10-20 methanol extraction polymkeric substance doubly, separates to remove and desolvates, and the gained precipitated product is drying to obtain final product.As react at the end polymkeric substance and precipitated and separate out, then do not need to add again methyl alcohol and precipitate, can directly separate solvent, the drying precipitated product that promptly gets.
Produce reaction medium used in the polyreaction of auto-synergistic effect high-molecular optical stablizer in the present invention and be meant benzene, toluene, chloroform, tetrahydrofuran (THF), heptane, in the organic solvent such as hexane, sherwood oil any, their consumption be the vinyl monomer total amount 2-4 doubly.
The high-molecular optical stablizer that contains the high-molecular optical stablizer of HA and HBP group on the side chain that makes with the inventive method simultaneously and only contain HA or HBP group has accordingly respectively carried out polyacrylic light stability test, comparing result shows under the HA condition identical with HBP concentration, the high-molecular optical stablizer that makes with the inventive method has better light stability, presents significant synergistic effect.
The auto-synergistic effect high-molecular optical stablizer of producing with the inventive method can be used as the photostabilizer of multiple synthetic polymer, as polyolefine or their multipolymer; Polyethylene, polypropylene, polybutene-1, polyhutadiene and b-propylene copolymer etc.; Polystyrene and multipolymer thereof, vinylformic acid and methacrylate based polymers and their multipolymer etc.
Embodiment 1
In a reaction flask that stirring, condenser, thermometer be installed, add 4-allyloxy-2,2,6,6-tetramethyl piperidine (M EHA) 17.8 grams, 4-allyloxy-2-dihydroxy benaophenonel (M EHBP) 2.5 gram and the 3rd monomers: vinyl acetate ester (VA) 25.8 grams add benzene again and make solution for 150 milliliters.Add Diisopropyl azodicarboxylate (AIBN) 0.5 gram, carry out polyreaction then under 80 ℃, the reaction times is 10 hours.React at the end, with 10 times of amount methanol extraction polymkeric substance, with the mensuration of dry laggard row element analysis of resulting polymers and light stability.
Embodiment 2-6
Method is with embodiment 1, produces with the listed proportioning of table 1 to contain M EHA, M EHBPAnd the terpolymer of vinyl acetate (VA):
Table 1 embodiment M EHAM EHBPVA benzene AIBN
(gram) (gram) (gram) (milliliter) (gram)
2?????15.8?????5.1?????25.8????150????0.5
3?????14.8?????6.4?????25.8????150????0.5
4?????13.0?????8.4?????25.8????150????0.5
5?????10.0?????12.7????25.8????150????0.5
6?????3.9??????20.3????25.8????150????0.5
Embodiment 7-8
With table 2 produce M to prescription EHA-VA or M EHBP-VA copolymer as a comparison.Method is all with embodiment 1.
Table 2 embodiment M EHAM EHBPVA benzene AIBN
(gram) (gram) (gram) (milliliter) (gram)
7???19.7???????????????43.1????20?????0.94
8????-????????14.8?????50??????20?????0.87
Embodiment 9
A certain amount of terpolymer that is made by embodiment 1-6 is made into benzene or acetone soln, adds the polypropylene powder of the no any auxiliary agent of 10 grams, making its content is 4 * 10 -5Mole/10 gram PP (polypropylene).Except that after desolvating, finish-drying, make the film that thickness is 100 ± 10 μ (pressing conditions: pressure 12MPa then, 185 ℃ of temperature, 1.5 minutes time, after the film forming in cold water rapid Cooling Quenching) (elimination (2900 part) irradiation is regularly followed the tracks of sample at 1712 centimetres with infrared spectra under the 500W high voltage mercury lamp with sample -1The carbonyl absorption, the time τ that reaches with carbonyl absorption at 0.01 o'clock is as photoxidation inductive phase of sample crystalline substance.
With above-mentioned same method embodiment 7-8 sample is carried out the test of light stability, the results are shown in Table 3.
I-VI represents in the table, each embodiment 1-6 sample is formed six comparative group with embodiment 7-8 sample respectively, in each comparative group, with the sample of embodiment 1-6 during as photostabilizer, in the polypropylene print effective concentration of HA and HBP respectively when making photostabilizer with the sample of embodiment 7 or 8 HA in the polypropylene print or the effective concentration of HBP equate.And the concentration sum of HA and HBP is 4 * 10 -5Mole/10 gram PP.
Synergistic effect can be used quantitative formula: S A=U 1+2-(τ 1+ τ 2) τ 1+ τ 2Represent that (Polym.Photochem.3.235,1983) wherein τ represent the oxidation induction period of polypropylene print.τ 1+2Expression contains the τ of the auto-synergistic effect high-molecular optical stablizer of the present invention of HA and HBP, t simultaneously 1Expression only contains the τ of the high-molecular optical stablizer of HA, τ 2Expression only contains the τ of the high-molecular optical stablizer of HBP.So work as S A=0 expression additive effect, S A＜0 expression negative synergism, S A＞0 expression synergistic effect.With the oxidation induction period τ that table 3 is listed, the synergistic effect S that the above-mentioned formula of substitution calculates AList in last, the result shows that high-molecular optical stablizer of the present invention has tangible auto-synergistic effect.
Table 3
The No sample 10 moles/10pp of content Oxidation induction period Synergistic effect S A％
I 1 embodiment, 12 comparative examples, 73 comparative examples 8 ????4 ????3.6 ????0.4 ????280 ????195 ????30 ????25
II 4 embodiment, 25 comparative examples, 76 comparative examples 8 ????4 ????2.8 ????1.2 ????400 ????170 ????50 ????82
III 7 embodiment, 38 comparative examples, 79 comparative examples 8 ????4 ????2.4 ????1.6 ????350 ????150 ????58 ????68
IV 10 embodiment, 4 11 comparative examples, 7 12 comparative examples 8 ????4 ????2 ????2 ????300 ????134 ????64 ????52
V 13 embodiment, 5 14 embodiment, 7 15 comparative examples 8 ????4 ????1 ????3 ????260 ????126 ????70 ????33
VI 16 embodiment, 6 17 embodiment, 7 18 comparative examples 8 ????4 ????0.4 ????3.6 ????150 ????55 ????80 ????11

Claims (9)

1. the preparation method who has the auto-synergistic effect high-molecular optical stablizer of hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group on the side chain, described photostabilizer is by monomer 4-allyloxy-2,2,6,6-tetramethyl piperidine (M EHA) and monomer 4-allyloxy-2-dihydroxy benaophenonel (M EHBP) and α-vinyl monomer as the 3rd monomer (M 3) copolymerization makes, and it is characterized in that described the 3rd class monomer comprises that general formula is: Acrylic or methacrylic esters of gallic acid monomer is R wherein 3For H or-CH 3, R 4Alkyl for 1-18 carbon;
Vinylbenzene and derivative thereof;
Maleic anhydride;
Acrylamide;
In vinyl cyanide and the vinyl acetate any, three kinds of monomeric ratio of components (weight %) are pressed
M 3∶(M EHA+M EHBP)＝80-0∶20-100，
M wherein EHA: M EHBP=90-10: 10-90,
Its preparation technology is as follows:
1.1 take by weighing monomer and be dissolved in the 2-4 times of organic solvent by described proportioning,
1.2 add the radical copolymerization initiator of reactant gross weight 0.2-5%, then
1.3 under agitation, temperature is 50-90 ℃ and carries out polymerization, reacted 6-10 hour,
1.4 reaction is at the end with 10-20 methanol extraction polymkeric substance doubly,
Desolvate 1.5 separate to remove,
1.6 with the precipitated product drying.
2. have the preparation method of the auto-synergistic effect high-molecular optical stablizer of hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group according to claim 1 on the side chain, it is characterized in that described M 3: (M EHA+ M EHBP)=70-0: 30-100, wherein (M EHA: M EHBA)=80-20: 20-80.
3. have the preparation method of the auto-synergistic effect high-molecular optical stablizer of hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group according to claim 1 on the side chain, it is characterized in that described M 3: (M EHA+ M EHBP) be 55: 45, M wherein EHA: M EHBPIt is 75: 25.
4. as having the preparation method of the auto-synergistic effect high-molecular optical stablizer of hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group on the side chain as described in the claim 1,2 or 3, it is characterized in that organic solvent used in 1.1 can be a benzene, toluene, chloroform, tetrahydrofuran (THF), heptane, hexane, any in the sherwood oil.
5. as having the preparation method of the auto-synergistic effect high-molecular optical stablizer of hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group on the side chain as described in the claim 1,2 or 3, it is characterized in that adding the 0.5-3% that the radical copolymerization initiator amount is the reactant gross weight.
6. as the preparation method of the auto-synergistic effect high-molecular optical stablizer that has hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group on claim 1, the 2 or 3 described side chains, it is characterized in that the radical copolymerization initiator is the 1-2% of reaction-ure mixture.
7. as having the preparation method of the auto-synergistic effect high-molecular optical stablizer of hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group on the side chain as described in the claim 1,2 or 3, it is characterized in that at 1.2 used initiators are dilauroyl peroxides.
8. as having the preparation method of the auto-synergistic effect high-molecular optical stablizer of hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group on the side chain as described in the claim 1,2 or 3, it is characterized in that at 1.2 used initiators are Diisopropyl azodicarboxylates, any in the 2,2'-Azobis(2,4-dimethylvaleronitrile).
9. as having the described preparation method of auto-synergistic effect high-molecular optical stablizer of hindered amine (HA) and O-hydroxyl-diphenyl ketone (HBP) group on claim 1,2 or 3 side chains, it is characterized in that the temperature of reaction in 1.3 is 60-70 ℃.
CN92110500A 1992-09-09 1992-09-09 Method for prepn. of high molecular stabilizator having self-concerted effect Expired - Fee Related CN1039420C (en)

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CN101993412B (en) * 2010-06-28 2012-07-04 北京天罡助剂有限责任公司 Hindered amine compound containing bis-benzophenone structure for light stabilizer and preparation method thereof
CN104231187B (en) * 2014-07-30 2016-12-07 广西师范学院 A kind of amphipathic pectination composite polymer light stabilizer and preparation method thereof
CN105601792A (en) * 2016-01-21 2016-05-25 四川大学 Preparation method of controllable molecular weight copolymerized hindered amine light stabilizer
CN109749113B (en) * 2019-01-25 2020-09-04 山东承坤信息科技有限公司 Long-life low-thermal conductivity thermal insulation material
CN111849028A (en) * 2020-06-22 2020-10-30 宿迁联盛科技股份有限公司 Graft polymerization type light stabilizer and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4311820A (en) * 1979-02-14 1982-01-19 Ciba-Geigy Corporation Homopolymers and copolymers of vinyl ethers of polyalkylpiperidinols and their use as stabilizers for plastics
US4390676A (en) * 1976-11-15 1983-06-28 Schering Corporation Ultraviolet absorbing lenses
EP0302406A2 (en) * 1987-08-03 1989-02-08 Kuraray Co., Ltd. Novel alternate copolymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4390676A (en) * 1976-11-15 1983-06-28 Schering Corporation Ultraviolet absorbing lenses
US4311820A (en) * 1979-02-14 1982-01-19 Ciba-Geigy Corporation Homopolymers and copolymers of vinyl ethers of polyalkylpiperidinols and their use as stabilizers for plastics
EP0302406A2 (en) * 1987-08-03 1989-02-08 Kuraray Co., Ltd. Novel alternate copolymers

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