WO2020259195A1 - 一种聚合型高分子空间位阻胺及其制备方法 - Google Patents

一种聚合型高分子空间位阻胺及其制备方法 Download PDF

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WO2020259195A1
WO2020259195A1 PCT/CN2020/092974 CN2020092974W WO2020259195A1 WO 2020259195 A1 WO2020259195 A1 WO 2020259195A1 CN 2020092974 W CN2020092974 W CN 2020092974W WO 2020259195 A1 WO2020259195 A1 WO 2020259195A1
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alkyl
group
atom
substituted
hindered amine
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PCT/CN2020/092974
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English (en)
French (fr)
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安晶晶
陈炜
高勇年
李靖
刘罡
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北京天罡助剂有限责任公司
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Priority to JP2021531334A priority Critical patent/JP7192182B2/ja
Priority to EP20831399.9A priority patent/EP3992230A4/en
Priority to US17/621,515 priority patent/US20220282044A1/en
Publication of WO2020259195A1 publication Critical patent/WO2020259195A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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

Definitions

  • the invention belongs to the field of polymer materials, and in particular relates to a polymeric polymer sterically hindered amine and a preparation method thereof.
  • the sterically hindered amine stabilizes polymers and their blends against light and/or heat damage, and It has beneficial effects as a flame retardant for polymers.
  • Light stabilizers are a class of compounds that can interfere with the physical and chemical process of photo-induced degradation of polymer materials, and are one of the most commonly used and important polymer material additives. Among them, hindered amine light stabilizers have received widespread attention due to their excellent anti-photoaging effects, and are the most active type of light stabilizers studied at home and abroad in the past two to thirty years.
  • Hindered amine light stabilizers include piperidine derivatives, imidazolone derivatives and azacycloalkanone derivatives. Piperidine derivatives have been studied more and have the fastest development. Many varieties have been supplied to the market, such as Tinuvin 770, Chimassorb 944, UV-3346, Chimassorb 2020 (EP782994), HS-950, Tinuvin 292, Tinuvin 119, UV-3529, HS-625, Tinuvin 123, Tinuvin NOR 371 (CN101484423A), Flamestab NOR 116 (US20110160453A1), FR-810 and so on.
  • Patent document CN105636954A discloses a triazine, piperidine and pyrrolidinyl hindered amine light stabilizer
  • patent document CN101048378A The synthesis method of N-alkoxyamine is disclosed.
  • Patent document CN102307940A discloses N-substituted macrocyclic triazine hydrogen ALS stabilizer.
  • Patent document CN1753871A discloses water-compatible sterically hindered alkoxyamine and hydroxyl substituted Alkoxyamine and so on.
  • hindered amine light stabilizers still have some shortcomings.
  • low molecular weight hindered amine light stabilizers are easily volatile during polymer processing; hindered amine light stabilizers have relatively poor thermal stability and are compared with polymers.
  • the poor compatibility between the substrates restricts the further application of hindered amine light stabilizers.
  • Patent US6599963 and WO99/00450 introduce the addition of hindered amine light stabilizers as flame retardants to polymer products.
  • Patent WO 99/00450 points out that the effect of hindered amine light stabilizers in thin products (such as films or fibers) is not ideal. The reasons are: on the one hand, the color of the hindered amine light stabilizer causes the final product to change color; on the other hand, it is hindered. The molecular weight of amine light stabilizer is relatively small, and it is easy to precipitate in polymer products. Therefore, in order to overcome these shortcomings, there is an urgent need to develop new alkoxy-substituted hindered amine light stabilizers, which can be used as both light stabilizers and flame retardants.
  • Patent US 8765848 introduces the grafting of alkoxy-substituted hindered amines on polyolefin waxes to obtain a new type of hindered amine light stabilizer.
  • These additives have high molecular weight, are not easy to precipitate, and have good compatibility with polyolefins.
  • the grafting rate is still not well controlled, which affects its flame retardancy and light stability for polymer products; moreover, because this type of hindered amine light stabilizer is grafted on polyolefin wax, it is combined with other This kind of resin still has the disadvantage of poor compatibility.
  • the inventors obtained a polymeric high molecular weight sterically hindered amine by subjecting the hindered amine light stabilizer to polymerization reaction.
  • the new sterically hindered amine has the advantages of high molecular weight, difficult migration in polymer products, good thermal stability, etc., and it can be compatible with different types of polymer materials by changing the substituents .
  • the repeating unit of the new sterically hindered amine contains anti-aging and flame retardant Structure, so the new sterically hindered amine has more efficient anti-aging and flame retardancy.
  • the object of the present invention is to provide a polymeric high molecular weight sterically hindered amine; another object of the present invention is to provide a method for preparing a polymeric high molecular weight sterically hindered amine; another object of the present invention is to provide a The use of a polymeric high molecular weight sterically hindered amine; another object of the present invention is to provide a composition containing a polymeric high molecular weight sterically hindered amine and its use.
  • the present invention provides a polymeric polymer sterically hindered amine, the general formula I of which is as follows:
  • m n represents the degree of polymerization of each monomer of the polymer, m n is an integer between 1-20; n is an integer between 1-20.
  • a 1, A 2, A 3 , A 4, A 5, A 6 ?? A n may be the same or different, the A 1, A 2, A 3 , A 4, A 5, A 6 « A n
  • the structure is selected from general formula II, III, IV or V,
  • G 1 and G 2 may be the same or different, and are independently selected from C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, phenyl, C 3 -C 12 cycloalkane Group or C 2 -C 12 heterocycloalkyl; or G 1 , G 2 and the carbon atoms between G 1 and G 2 form a C 3 -C 12 cycloalkyl group, where alkyl, alkenyl, alkynyl, benzene Any hydrogen atom on the group, cycloalkyl or heterocycloalkyl group can be substituted by hydroxyl, -NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 or -COR 21 , the hetero The heteroatoms in the ring can be oxygen, nitrogen, sulfur, phosphorus or silicon.
  • G 1 and G 2 are independently selected from C 1 -C 4 alkyl groups.
  • G 1 and G 2 are independently selected from methyl groups.
  • Said R 21 is selected from hydrogen, unsubstituted or substituted C 1 -C 18 alkyl-substituted C 1 -C 40 alkyl; unsubstituted or optionally substituted with 1-3 -OH, a hydrogen atom or C 1-30 A phenyl group substituted by an alkyl group, an unsubstituted or a C 7-9 phenyl alkyl group in which any hydrogen atom on the phenyl group is substituted with 1-3 -OH or C 1-30 alkyl groups.
  • the R 21 is selected from C 1 -C 20 alkyl.
  • said R 21 is selected from C 1 -C 12 alkyl.
  • E is selected from -CO- or -(CH 2 ) a -, a is selected from 0, 1, or 2,
  • E is selected from -CO- or -CH 2 -.
  • R 1 and R 2 may be the same or different, and are independently selected from hydrogen, C 1 -C 50 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 heterocycloalkyl, wherein the alkyl,
  • the H atom in cycloalkyl and heterocycloalkyl can be substituted by hydroxyl, -NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 or -COR 21.
  • the heteroatom of can be oxygen, nitrogen, sulfur, phosphorus or silicon, and the value of R 21 is as described above.
  • R 3 is selected from C 1 -C 50 alkylene, C 3 -C 12 cycloalkylene, C 2 -C 12 heterocycloalkylene, wherein the alkylene, cycloalkylene, heterocyclic alkylene
  • the H atom in the alkyl group can be substituted by hydroxyl, NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 or -COR 21
  • the heteroatom in the heterocyclic ring can be oxygen, Nitrogen, sulfur, phosphorus or silicon.
  • the total number of carbon atoms in R 1 , R 2 and R 3 is 50 or less.
  • the R 1 and R 2 are independently selected from hydrogen and C 1 -C 40 alkyl groups, wherein the H atom in the alkyl group can be replaced by -R 21 , -OR 21 , -COOR 21 or -COR 21 replaced.
  • the R 3 is selected from a C 1 -C 40 alkylene group, wherein the H atom in the alkylene group may be substituted by -R 21 , -OR 21 , -COOR 21 or -COR 21 .
  • the total number of carbon atoms in R 1 , R 2 and R 3 is less than or equal to 40.
  • Q 1 and Q 2 can be the same or different, independently selected from -O-, -O-CO-O-, -CO-O-, -CO-NR 22 -, -NR 22 -, -NR 22 -CO- NR 23 -or-(CH 2 ) b -, b is 0, 1, or 2.
  • said Q 1 and Q 2 are independently selected from -O-, -CO-O-, -CO-NR 22 -or -NR 22 -.
  • Q 1 and Q 2 are independently selected from -CO-O-, -CO-NR 22 -or -NR 22 -.
  • said R 22 and R 23 are independently selected from hydrogen, unsubstituted or C 1 -C 40 alkyl group in which any hydrogen atom is substituted by C 1 -C 18 alkyl group, and unsubstituted or any hydrogen atom is 1 -3 -OH or C 1-30 alkyl group substituted phenyl group, unsubstituted or phenyl group with any hydrogen atom substituted by 1-3 -OH and C 1-30 alkyl group C 7-9 Phenylalkyl.
  • said R 22 and R 23 are independently selected from hydrogen and C 1 -C 20 alkyl.
  • said R 22 and R 23 are independently selected from hydrogen and C 1 -C 12 alkyl.
  • T is selected from: unsubstituted or C 1 -C 10 alkylene substituted by C 1 -C 5 alkyl,
  • T in the structural formula is a repeatable unit, and the next T group is connected between Q 1 and Q 2 ;
  • n m p is an integer between 1-20.
  • R 7 and R 8 may be the same or different, and are selected from hydrogen, C 1 -C 40 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 heterocycloalkyl, wherein the alkyl, cycloalkane
  • the H atom in the group and heterocycloalkyl group can be substituted by hydroxyl, NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 or -COR 21.
  • the heteroatoms in the heterocyclic ring can be Is oxygen, nitrogen, sulfur, phosphorus, or silicon.
  • R 7 , R 8 and the N atom between R 7 and R 8 form a C 3 -C 12 cycloalkylene group or a C 2 -C 12 heterocycloalkylene group, wherein the cycloalkylene group, the heterocyclic ring
  • the H atom in the alkylene group can be substituted by hydroxyl, NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 or -COR 21.
  • the heteroatom in the heterocyclic ring can be oxygen, Nitrogen, sulfur, phosphorus or silicon.
  • said R 7 and R 8 are independently selected from hydrogen, unsubstituted or substituted C 1 -C 20 alkyl groups with -R 21 ; or R 7 , R 8 and R 7 and R 8 The N atom forms an unsubstituted C 3 -C 12 cycloalkylene or C 2 -C 12 heterocycloalkylene.
  • the C 2 -C 12 heterocycloalkylene group is preferably a C 2 -C 12 oxygen-containing heterocycloalkylene group.
  • said R 7 and R 8 are independently selected from unsubstituted C 1 -C 20 alkyl groups; or R 7 , R 8 and the N atom between R 7 and R 8 An unsubstituted C 3 -C 10 cycloalkylene or C 2 -C 8 oxygen-containing cycloalkylene is formed.
  • Q 3 is selected from -O-, -O-CO-O-, -CO-O-, -CO-NR 22 -, -NR 22 -, -NR 22 -CO-NR 23 -or-(CH 2 ) b -, b is 0, 1, or 2.
  • the Q 3 is selected from -O-, -CO-O-, -CO-NR 22 -or -NR 22 -.
  • Q 3 is independently selected from -NR 22 -, and the values of R 22 and R 23 are as described above.
  • R 4 and R 5 may be the same or different, and are independently selected from hydrogen, C 1 -C 50 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 heterocycloalkyl, wherein the alkyl,
  • the H atom in cycloalkyl and heterocycloalkyl can be substituted by hydroxyl, -NO 2 , halogen, amino, cyano, -R 21 , -COOR 21 or -COR 21 , and the heteroatoms in the heterocyclic ring can be It is oxygen, nitrogen, sulfur, phosphorus or silicon, and the value of R 21 is as described above.
  • R 6 is selected from C 1 -C 50 alkylene, C 3 -C 12 cycloalkylene, C 2 -C 12 heterocycloalkylene, wherein the alkylene, cycloalkylene, heterocyclic alkylene
  • the H atom in the alkyl group can be substituted by hydroxyl, NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 or -COR 21
  • the heteroatom in the heterocyclic ring can be oxygen, Nitrogen, sulfur, phosphorus or silicon.
  • the total number of carbon atoms in R 4 , R 5 and R 6 is 50 or less.
  • the R 4 and R 5 are independently selected from hydrogen and C 1 -C 40 alkyl groups, wherein the H atom in the alkyl group may be -R 21 , -OR 21 , -COOR 21 or -COR 21 replaced.
  • the R 6 is selected from a C 1 -C 40 alkylene group, wherein the H atom in the alkylene group may be substituted by -R 21 , -OR 21 , -COOR 21 or -COR 21 .
  • the total number of carbon atoms in R 4 , R 5 and R 6 is less than or equal to 40.
  • S 1 is selected from -CH 2 -, -CO- or -NR 24 -;
  • S 2 is selected from N or C
  • S 3 is selected from -O-, -CH 2 -, -CO- or -NR 24 -;
  • R 24 is selected from hydrogen, C 1 -C 50 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 heterocycloalkyl, wherein the alkyl group, cycloalkyl group, heterocycloalkyl group
  • the H atom can be substituted by hydroxyl, -NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 or -COR 21 ;
  • the heteroatom in the heterocyclic ring can be oxygen, nitrogen, sulfur , Phosphorus or silicon;
  • w is selected from an integer between 1-20
  • z is selected from an integer between 2-20.
  • S 1 is selected from -CH 2 -, -CO-;
  • S 2 is selected from N;
  • S 3 is selected from -O-, -CH 2 -, -CO-;
  • w is selected from an integer between 1-7, and z is selected from an integer between 2-5.
  • U is selected from R 24 or
  • U in the structural formula is a repeatable unit, and S 2 is connected to the next U group;
  • g is selected from an integer between 0-20
  • h is selected from an integer between 1-20
  • V is selected from Among them, the values of Q 2 and T are as described above.
  • R 12 and R 13 are the end-capping groups of the polymer.
  • the R 12 and R 13 may be the same or different, and are independently selected from hydrogen, unsubstituted or any H atom by hydroxyl, -NO 2 , halogen, amino, Cyano group, -R 21 , -OR 21 , -COOR 21 , -COR 21 or C 4 -C 30 alkyl substituted with C 1 -C 10 alkyl, unsubstituted or any H atom is hydroxy, -NO 2 , Halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 , -COR 21 or phenyl substituted with a C 1-30 alkyl group, unsubstituted or any H atom of the phenyl group is hydroxyl,- NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 , -COR 21 or
  • said R 12 and R 13 are independently selected from hydrogen, unsubstituted or any H atom is substituted by hydroxyl, -NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 ,- COR 21 or C 4 -C 30 alkyl substituted with C 1 -C 10 alkyl, s-triazinyl substituted with two -NR 7 R 8 .
  • said R 12 and R 13 are independently selected from hydrogen, unsubstituted or any H atom is substituted by hydroxyl, -NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 , -COR 21 or C 4 -C 30 alkyl substituted with C 1 -C 10 alkyl.
  • the A 1, A 2, A 3 , A 4, A 5, A 6 ?? A n is selected from the following formulas:
  • the carbon chain with more than 4 C atoms generates an activation point under the action of the catalyst and reacts with the O connected to the piperidine ring.
  • a and B are functional groups with linkage function respectively.
  • the concept of hyperbranched polymers was proposed at the end of the 19th century and is still being widely studied.
  • the polymeric polymer sterically hindered amine of the general formula I can be selected from the following polymerization forms:
  • the polymer When the polymer is polymerized as AB, it forms a linear polymer, which is simply expressed as ABAB; when the polymer is polymerized as AB 2 , it forms a hyperbranched polymer, which is simply expressed as the structure on the right.
  • the polymeric polymer sterically hindered amine of the general formula I can also be selected from the following polymerization forms:
  • m n represents the degree of polymerization of each monomer of the polymer, which may be the same or different, and m n is an integer between 1-20.
  • R 1 and R 2 are independently selected from hydrogen or C 1 -C 40 alkyl; R 3 is selected from C 1 -C 40 alkylene; the total number of carbon atoms in R 1 , R 2 and R 3 is less than Equal to 40.
  • R 22 is selected from C 1 -C 5 alkyl.
  • R 7 and R 8 are independently selected from C 1 -C 10 alkylene groups, or R 7 , R 8 and the N atom between R 7 and R 8 form a C 3 -C 10 cycloalkylene group and C 2 -C 8 Oxygen-containing cycloalkylene.
  • R 4 and R 5 are independently selected from hydrogen or C 1 -C 40 alkyl; R 6 is selected from C 1 -C 40 alkylene; the total number of carbon atoms in R 4 , R 5 and R 6 is less than or equal to 40.
  • Q 1 and Q 2 are independently selected from -CO-O-, -CO-NR 22 -or -NR 22 -, and R 22 is selected from C 1 -C 5 alkyl.
  • alkyl includes carbon atoms within a given range, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert Butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl Base, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl , 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5, 5-hexamethylhexyl.
  • alkenyl groups are vinyl, allyl and butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, ten Branched and straight-chain isomers of a carbalkenyl and dodecenyl.
  • alkenyl also includes groups with more than one conjugated or non-conjugated double bond, for example, it may contain one double bond.
  • cycloalkyl examples include cyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, trimethylcyclopentyl, ethylcyclopentyl , Propylcyclopentyl, isopropylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl.
  • heterocycloalkyl groups are cycloalkyl groups containing elements such as N, O, S, Si.
  • alkylene groups are ethylene, propylene, isopropylidene, butylene, sec-butylene, isobutylene, 2-ethylbutylene, pentylene within the range of given carbon atoms Group, isopentylene, 1-methylpentylene, 1,3-dimethylbutylene, hexylene, 1-methylhexylene, heptylene, 1,1,3,3-tetramethyl Butylene, 1-methylheptylene, 3-methylheptylene, octylene, 2-ethylhexylene, 1,1,3-trimethylhexylene, 1,1,3,3- Branched and linear isomers of tetramethylpentylene, nonylidene, decylene, undecylene, and dodecylene.
  • the C 7-9 phenylalkyl group in the present invention is preferably benzyl and 2-phenethyl.
  • the C 7-9 phenyl alkyl substituted by 1-3 C 1-4 alkyl groups in the present invention is preferably methyl benzyl, dimethyl benzyl, trimethyl benzyl or tertiary Butyl benzyl.
  • the invention provides a method for preparing a polymeric polymer sterically hindered amine of general formula I, which comprises
  • the polymerizable monomer is dissolved in a solvent or heated to a molten state, and the catalyst and hydroperoxide are sequentially added to react to form the polymerizable polymer sterically hindered amine described in general formula I.
  • the general structure of the polymerizable monomer is as follows Shown:
  • R and R' may be the same or different, and are selected from C 1 -C 50 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 heterocycloalkyl, wherein the alkyl, cycloalkyl, hetero
  • the H atom in the cycloalkyl group can be substituted by hydroxyl, NO 2 , halogen, amino, cyano, -R 21 , -OR 21 , -COOR 21 or -COR 21 , and the heteroatom in the heterocyclic ring may be oxygen , Nitrogen, sulfur, phosphorus or silicon; and, the number of carbon atoms in R and R'is less than or equal to 50; the values of other parameters in the general formula are as described above.
  • the polymerizable monomers shown above are known in the art, and some are commercially available, or can be synthesized according to methods known in the art.
  • the solvent used in the method of the present invention is common organic solvents such as aromatic hydrocarbons (such as benzene, dichlorobenzene, chlorobenzene, etc.), halogenated hydrocarbons, alcohols (such as methanol, ethanol, ethylene glycol or methyl ether), or water.
  • aromatic hydrocarbons such as benzene, dichlorobenzene, chlorobenzene, etc.
  • halogenated hydrocarbons such as methanol, ethanol, ethylene glycol or methyl ether
  • alcohols such as methanol, ethanol, ethylene glycol or methyl ether
  • the solvent is aromatic hydrocarbon solvents such as benzene, dichlorobenzene, and chlorobenzene.
  • the reaction temperature in the method of the present invention is 0-250°C, preferably 25-100°C, more preferably 45-150°C.
  • the catalyst used in the method of the present invention is a metal compound, wherein the metal in the metal compound is selected from the group IVb, Vb, VIb, VIIb and VIII metal elements of the periodic table.
  • the metal compound is selected from vanadyl acetylacetonate, vanadium acetylacetonate (trivalent), cobalt carbonyl, chromium oxide (hexavalent), n-butyl titanate, isopropyl titanate, molybdenum hexacarbonyl, tri Molybdenum oxide, vanadium pentoxide, chromium trioxide and/or tungsten trioxide.
  • the metal compound is molybdenum trioxide, vanadium pentoxide, chromium trioxide and/or tungsten trioxide.
  • the amount of the catalyst used in the present invention is 0.0001 to 0.6 molar equivalent, preferably 0.01 to 0.3 molar equivalent, more preferably 0.01 to 0.15 molar equivalent, based on the molar equivalent of the polymerizable monomer.
  • the hydroperoxide used in the method of the present invention is an inorganic hydroperoxide or an organic hydroperoxide.
  • the inorganic hydroperoxide is H 2 O 2 ; the organic hydroperoxide is alkyl hydroperoxide and aryl hydroperoxide.
  • the alkyl hydroperoxide is a tertiary alkyl hydroperoxide, such as tert-butyl hydroperoxide, tert-amyl hydroperoxide, tert-hexyl hydroperoxide or tert-octyl hydroperoxide;
  • the aryl hydroperoxide mentioned is ethylbenzene hydroperoxide, tetralin peroxide or cumene hydroperoxide.
  • the hydroperoxide is selected from H 2 O 2 , tert-butyl hydroperoxide or cumene hydroperoxide.
  • the amount of hydroperoxide used in the present invention is 1-20 molar equivalents, preferably 1-10 molar equivalents, more preferably 1-5 molar equivalents, based on the molar equivalents of the polymerizable monomers.
  • the method of the invention is carried out in an inert atmosphere such as nitrogen, helium or argon.
  • the method of the invention can be carried out at 0.5-30 bar, preferably 0.5-20 bar, especially 0.5-10 bar, or under ambient pressure.
  • the present invention provides the use of a polymeric polymer sterically hindered amine with the general formula I as a stabilizer and/or flame retardant.
  • the polymeric polymer sterically hindered amine of general formula I has a stabilizing and/or flame retardant effect on organic substances that are sensitive to light, heat or oxidation.
  • the present invention provides a composition comprising one or more organic substances sensitive to light, heat or oxidation and at least one polymeric polymer sterically hindered amine with the general formula I.
  • the composition further includes one or a combination of two or more of antioxidants, UV absorbers, hindered amine light stabilizers, enhancers, fillers, flame retardants or other additives.
  • the other additives are selected from: plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, fire retardants, antistatic agents and foaming agents.
  • the amount of the polymerized polymer sterically hindered amine of general formula I is determined by the nature of the organic substance, the end use and additives, and the polymerized polymer sterically hindered amine of general formula I Can be used in various proportions.
  • the amount of the polymeric polymer sterically hindered amine with the general formula I is 0.01%-5% by weight of the organic substance;
  • the amount of the polymeric polymer sterically hindered amine with the general formula I is 0.05%-2% by weight of the organic substance;
  • the amount of the polymeric polymer sterically hindered amine with the general formula I is 0.05%-1% by weight of the organic substance.
  • the organic substance is selected from: polyolefin, acrylonitrile/butadiene/styrene, polyvinyl chloride, polymethyl methacrylate, polyacetal, polyamide, polyimide, epoxy resin, polyurethane, poly One or a combination of two or more of carbonate, polyurethane, polyester, polysulfone, polyurea, polystyrene, thermoplastic elastomer, and ethylene-vinyl acetate copolymer.
  • the polyolefin is selected from polyethylene or polypropylene containing a rubber phase based on ethylene and/or propylene.
  • the polyacetal includes polyoxymethylene, polyoxymethylene containing ethylene oxide as a comonomer, and polyacetal modified with thermoplastic polyurethane, acrylate or MBS.
  • the polyamides include polyamides and copolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or corresponding lactams, such as polyamide 4, polyamide 6, polyamide 66, polyamide 610 , Polyamide 69, polyamide 612, polyamide 46, polyamide 1212, polyamide 11, polyamide 12, aromatic polyamide derived from meta-xylene diamine and adipic acid; from hexamethylene and metabenzene Polyamides obtained by dicarboxylic acid or/and terephthalic acid in the presence or absence of elastomers as modifiers.
  • polyamides and copolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or corresponding lactams such as polyamide 4, polyamide 6, polyamide 66, polyamide 610 , Polyamide 69, polyamide 612, polyamide 46, polyamide 1212, polyamide 11, polyamide 12, aromatic polyamide derived from meta-xylene diamine and a
  • the polyesters include polyesters derived from dicarboxylic acids and glycols and/or from hydroxycarboxylic acids or their corresponding lactones, such as polyethylene terephthalate and polybutylene terephthalate.
  • the thermoplastic elastomers include polyolefin thermoplastic elastomers and block copolymer type polystyrene thermoplastic elastomers.
  • Polyolefin thermoplastic elastomers include polyolefin resins (such as polyethylene and polypropylene serving as hard segments) and rubber compositions (such as ethylene-propylene-diene elastomer (EPDM) serving as soft segments).
  • EPDM ethylene-propylene-diene elastomer
  • the block copolymer type polystyrene thermoplastic elastomer includes polystyrene serving as a hard segment and polydiene (such as polybutadiene or polyisoprene) serving as a soft segment.
  • thermoplastic elastomer a blend of polyolefin elastomer and polystyrene elastomer may also be used as the thermoplastic elastomer of the present invention.
  • the methods used to combine the soft segment and the hard segment in the thermoplastic elastomer can be roughly divided into simple blending, implantation through copolymerization, and dynamic crosslinking.
  • the combination of polystyrene thermoplastic elastomer segments includes SBS, SIS, SEBS, SEPS, hydrogenated polymers of any of these four copolymers, hydrogenated polymers of SBR (HSBR) and polypropylene and selected from these polymers A blend of one or more arbitrary members.
  • the antioxidant is selected from: phenol and/or amine antioxidants, phosphites, thioesters and the like.
  • antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168 and the like are preferred.
  • the UV absorber is selected from: salicylate, benzoate, benzophenone, benzotriazole, triazine ultraviolet absorber.
  • the hindered amine light stabilizer is selected from: hindered amine light stabilizers having a different structure from the compound of the present invention or a mixture thereof, such as bis(2,2,6,6-tetramethyl-4-piperidinyl)decane Ester, succinic acid and polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, Chimassorb 944, Chimassorb 2020, UV-3346, UV-3529, Tinuvin 770, Tinuvin622LD , Tinuvin 292, HS-625, Hindered amine light stabilizer such as HS-950.
  • hindered amine light stabilizers having a different structure from the compound of the present invention or a mixture thereof such as bis(2,2,6,6-tetramethyl-4-piperidinyl)decane Ester, succinic acid and polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, Chimassorb 944, Chimassorb 2020, UV-3346,
  • the fillers and reinforcing agents are selected from calcium carbonate, silicate, glass fiber, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder and Flour or other natural product fibers, synthetic fibers.
  • the present invention provides an application of the composition in the preparation of any polymer material products.
  • the polymer materials such as plastics, coatings, adhesives, etc., are selected from: interior or exterior decoration materials of automobiles, floating devices, road traffic Devices, agricultural products, electrical appliances, furniture, footwear, sanitary products, and healthcare products.
  • the plastic products can be manufactured by any method known to those of ordinary skill in the art, including but not limited to extrusion, extrusion blow molding, film casting, calendering, injection molding, blow molding, compression molding, thermoforming, spinning molding , Blow-extrusion and rotary casting.
  • Standard polymer 79.8wt% thermoplastic polypropylene; 20wt% hydrotalcite; 0.20wt% antioxidant (AO-1010);
  • 1# is 100wt% standard polymer
  • 2# is 99.7wt% standard polymer, 0.3wt% sterically hindered amine (Example 3);
  • 3# is 99.7wt% standard polymer, 0.3wt% sterically hindered amine (Example 5);
  • 4# is 99.7wt% standard polymer, 0.3wt% sterically hindered amine (Example 6);
  • 5# is 99.7wt% standard polymer, 0.3wt% sterically hindered amine (Example 8);
  • 6# is 99.7wt% standard polymer, 0.3wt% sterically hindered amine (Example 13);
  • Example 14 is 99.7wt% standard polymer, 0.4wt% sterically hindered amine (Example 14);
  • 8# is 99.7wt% standard polymer, 0.3wt% sterically hindered amine (Example 15);
  • Standard polymer 79.8wt% thermoplastic polyethylene; 20wt% calcium carbonate; 0.20wt% antioxidant (AO-1010);
  • 1# is 100wt% standard polymer
  • 2# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 3);
  • 3# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 5);
  • 4# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 6);
  • 5# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 8);
  • 6# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 13);
  • Example 14 is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 14);
  • 8# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 15);
  • thermoplastic polyvinyl chloride 65.5wt% thermoplastic polyvinyl chloride; 31.5wt% plasticizer; 1.6wt% epoxy soybean oil; 1.4wt% calcium zinc stabilizer;
  • 1# is 100wt% standard polymer
  • 2# is 99.5wt% standard polymer, 0.25wt% UV-531; 0.25wt% sterically hindered amine (Example 3);
  • 3# is 99.5wt% standard polymer, 0.25wt% UV-531; 0.25wt% sterically hindered amine (Example 5);
  • 4# is 99.5wt% standard polymer, 0.25wt% UV-531; 0.25wt% sterically hindered amine (Example 6);
  • 5# is 99.5wt% standard polymer, 0.25wt% UV-531; 0.25wt% sterically hindered amine (Example 8);
  • Standard polymer 79.8wt% thermoplastic polyamide 6; 20wt% calcium carbonate; 0.20wt% antioxidant (AO-1098);
  • 1# is 100wt% standard polymer
  • 2# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 3);
  • 3# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 9);
  • 4# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 10);
  • 5# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 11);
  • 6# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 12);
  • 1# is 100wt% standard polymer
  • 2# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 3);
  • 3# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 5);
  • 4# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 6);
  • 5# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 8);
  • 1# is 100wt% standard polymer
  • 2# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 3);
  • 3# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 9);
  • 4# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 10);
  • 5# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 11);
  • 6# is 99.6wt% standard polymer, 0.4wt% sterically hindered amine (Example 12);

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Abstract

通式为Ⅰ的聚合型高分子空间位阻胺，所述空间位阻胺具有分子量高、在聚合物制品中不易迁出、热稳定性好等优点，对光、热或氧化敏感的有机物质具有稳定和/或阻燃的作用，而且可以通过改变取代基，使其与不同种类的高分子材料都具有较好的相容性。

Description

一种聚合型高分子空间位阻胺及其制备方法 技术领域
本发明属于高分子材料领域，特别涉及一种聚合型高分子空间位阻胺及其制备方法，所述空间位阻胺在稳定聚合物及其共混物防止光和/或热的侵害，以及作为聚合物的阻燃剂方面具有有益效果。
背景技术
高分子材料在加工、贮存和使用的过程中，普遍存在其物理性质、化学性质和力学性能会逐渐变差的现象。例如塑料的发黄、脆化与开裂；橡胶的发粘、硬化、龟裂及绝缘性能下降。纤维制品的变色、褪色、强度降低、断裂等现象。这些现象统称为高分子材料的老化或者降解。造成高分子材料老化的因素很多，其中以氧、光和热的影响最为显著。为了防止或延缓其老化，延长其使用寿命，人们通常将一些具有特定功能的化学助剂添加到高分子材料中。光稳定剂就是一类能够干预高分子材料光诱导降解物理化学过程的化合物，是最常用也是最重要的高分子材料添加剂之一。其中，受阻胺光稳定剂因其优异的防光老化效果受到广泛的关注，是近二、三十年来国内外研究最活跃的一类光稳定剂。
受阻胺光稳定剂有：哌啶衍生物、咪唑酮衍生物和氮杂环烷酮衍生物等系列。哌啶衍生物研究得比较多，发展也最快，已有不少品种供应市场，如Tinuvin 770、Chimassorb 944、UV-3346、Chimassorb 2020(EP782994)、
Figure PCTCN2020092974-appb-000001
HS-950、Tinuvin 292、Tinuvin 119、UV-3529、
Figure PCTCN2020092974-appb-000002
HS-625、Tinuvin 123、Tinuvin NOR 371(CN101484423A)、Flamestab NOR 116(US20110160453A1)、
Figure PCTCN2020092974-appb-000003
FR-810等。
除了以上已经商业化产品，各国科研人员也在积极研究一些具有新结构的受阻胺光稳定剂：专利文献CN105636954A公开了一种三嗪、哌啶和吡咯烷基受阻胺光稳定剂，专利文献CN101048378A公开了N-烷氧基胺的合成方法，专利文献CN102307940A公开了N-取代的大环三嗪氢ALS稳定剂，专利文献CN1753871A公开了水相容的空间位阻烷氧基胺和羟基取代的烷氧基胺等。
然而，目前为止，受阻胺光稳定剂仍然存在一些缺点，如在聚合物加工过程中，低分 子量的受阻胺光稳定剂易挥发；受阻胺光稳定剂的热稳定性相对较差、与聚合物基体之间的相容性较差等，这些制约了受阻胺光稳定剂的进一步应用。
另外，越来越多的应用领域要求高分子材料具有阻燃性，其中，应用最广的阻燃剂主要是溴类和磷类化合物。但是，为了达到阻燃效果，这些阻燃剂的添加量较高，进而影响高分子材料的其他性能；而且在一些薄型制品中，即使阻燃剂添加量较高，依然达不到阻燃效果。近些年，研究发现除了作为光稳定剂以外，烷氧基取代的受阻胺光稳定剂还可以作为阻燃剂。
专利US 6599963和WO 99/00450介绍了将受阻胺光稳定剂作为阻燃剂加入到聚合物制品中。专利WO 99/00450指出受阻胺光稳定剂在薄型制品(如薄膜或纤维中)的效果不理想，其原因为：一方面由于受阻胺光稳定剂自身颜色导致最终制品变色；另一方面由于受阻胺光稳定剂的分子量相对较小，在聚合物制品中易析出。因此，为了克服这些缺点，急需开发新型的烷氧基取代受阻胺光稳定剂，既可以作为光稳定剂又可以作为阻燃剂。
专利US 8765848介绍了将烷氧基取代的受阻胺接枝在聚烯烃蜡上，得到了新型的受阻胺光稳定剂。这类助剂具有较高分子量、不易析出、且与聚烯烃相容性好。但是，仍存在无法很好控制接枝率，从而影响其对于聚合物制品的阻燃性和光稳定性；而且，由于是将该类受阻胺光稳定剂接枝在聚烯烃蜡上，所以与其他种类的树脂仍然存在相容性差的缺点。
在本发明中，发明人通过将受阻胺光稳定剂进行聚合反应，得到一种聚合型的高分子量空间位阻胺。该新型空间位阻胺具有分子量高、在聚合物制品中不易迁出、热稳定性好等优点，而且可以通过改变取代基，使其与不同种类的高分子材料都具有较好的相容性。
另外，由于该新型的空间位阻胺的重复单元中包含对防老化和阻燃起作用的
Figure PCTCN2020092974-appb-000004
结构，所以该新型空间位阻胺具有更加高效的防老化性和阻燃性。
发明内容
本发明的目的是提供一种聚合型的高分子量空间位阻胺；本发明的另一个目的是提供一种聚合型的高分子量空间位阻胺的制备方法；本发明的另一个目的是提供一种聚合型的高分子量空间位阻胺的用途；本发明还一个目的是提供一种包含聚合型的高分子量空间位阻胺的组合物及其用途。
本发明提供一种聚合型高分子空间位阻胺，其通式Ⅰ如下：
Figure PCTCN2020092974-appb-000005
其中，m n表示聚合物各单体的聚合度，m n为1-20之间的整数；n为1-20之间的整数。
A 1、A 2、A 3、A 4、A 5、A 6……A n可以相同也可以不同，所述A 1、A 2、A 3、A 4、A 5、A 6……A n结构选自通式Ⅱ、Ⅲ、Ⅳ或Ⅴ，
Figure PCTCN2020092974-appb-000006
其中，G 1与G 2可以相同或不同，独立的选自C 1-C 18烷基、C 2-C 18烯基、C 2-C 18炔基、苯基、C 3-C 12环烷基或C 2-C 12杂环烷基；或者G 1、G 2与G 1和G 2之间的碳原子形成C 3-C 12环烷基，其中烷基、烯基、炔基、苯基、环烷基或杂环烷基上任意氢原子可以被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅。
优选的，G 1、G 2独立的选自C 1-C 4烷基。
更优选的，G 1、G 2独立的选自甲基。
所述的R 21选自氢、未经取代或被C 1-C 18烷基取代的C 1-C 40烷基；未经取代或任意氢 原子被1-3个-OH或C 1-30烷基基团取代的苯基、未经取代或苯基上任意氢原子被1-3个-OH或C 1-30烷基基团取代的C 7-9苯基烷基。
优选的，所述的R 21选自C 1-C 20烷基。
更优选的，所述的R 21选自C 1-C 12烷基。
E选自-CO-、或-(CH 2) a-，a选自0、1、或2，
优选的，E选自-CO-、或-CH 2-。
R 1、R 2可以相同或不同，独立的选自氢、C 1-C 50烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中的H原子可被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅，R 21取值如前所述。
R 3选自C 1-C 50亚烷基、C 3-C 12环亚烷基、C 2-C 12杂环亚烷基，其中，所述亚烷基、环亚烷基、杂环亚烷基中的H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅。
并且，R 1、R 2和R 3中碳原子数的总和小于等于50。
优选的，所述R 1和R 2独立的选自氢、C 1-C 40烷基，其中，所述烷基中的H原子可被-R 21、-OR 21、-COOR 21或-COR 21取代。
优选的，所述R 3选自C 1-C 40亚烷基，其中，所述亚烷基中的H原子可被-R 21、-OR 21、-COOR 21或-COR 21取代。
优选的，所述的R 1、R 2和R 3中碳原子数的总和小于等于40。
Q 1与Q 2可以相同或不同，独立的选自-O-、-O-CO-O-、-CO-O-、-CO-NR 22-、-NR 22-、-NR 22-CO-NR 23-或-(CH 2) b-，b是0、1、或2。
优选的，所述的Q 1、Q 2独立的选自-O-、-CO-O-、-CO-NR 22-或-NR 22-。
在本发明的优选实施方式中，Q 1、Q 2独立的选自-CO-O-、-CO-NR 22-或-NR 22-。
其中，所述的R 22、R 23独立的选自氢、未经取代或任意氢原子被C 1-C 18烷基取代的C 1-C 40烷基，未经取代或任意氢原子被1-3个-OH或C 1-30烷基基团取代的苯基、未经取代 或苯基任意氢原子被1-3个-OH和C 1-30烷基基团取代的C 7-9苯基烷基。
优选的，所述的R 22、R 23独立的选自氢、C 1-C 20烷基。
更优选的，所述的R 22、R 23独立的选自氢、C 1-C 12烷基。
T的结构式选自：未经取代或被C 1-C 5烷基取代的C 1-C 10亚烷基、
Figure PCTCN2020092974-appb-000007
其中T的结构式为
Figure PCTCN2020092974-appb-000008
时，结构式中的T为可重复单元，Q 1和Q 2之间连接下一个T基团；
m p为1-20之间的整数。
R 7、R 8可以相同或不同，选自氢、C 1-C 40烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅。
或者R 7、R 8与R 7和R 8之间的N原子形成C 3-C 12环亚烷基、C 2-C 12杂环亚烷基，其中，所述环亚烷基、杂环亚烷基中H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅。
优选的，所述的R 7和R 8独立的选自氢、未经取代或被-R 21取代的C 1-C 20烷基；或者R 7、R 8与R 7和R 8之间的N原子形成未经取代的C 3-C 12环亚烷基或C 2-C 12杂环亚烷基。
优选的，所述的C 2-C 12杂环亚烷基优选为C 2-C 12含氧杂环亚烷基。
在本发明的优选实施方式中，所述的R 7和R 8独立的选自未经取代的C 1-C 20烷基；或者R 7、R 8与R 7和R 8之间的N原子形成未经取代的C 3-C 10环亚烷基或C 2-C 8含氧环亚烷基。
Q 3选自-O-、-O-CO-O-、-CO-O-、-CO-NR 22-、-NR 22-、-NR 22-CO-NR 23-或-(CH 2) b-，b是0、1、或2。
优选的，所述的Q 3选自-O-、-CO-O-、-CO-NR 22-或-NR 22-。
在本发明的优选实施方式中，Q 3独立的选自-NR 22-，R 22、R 23的取值如前所述。
R 4、R 5可以相同或不同，独立的选自氢、C 1-C 50烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中的H原子可被羟基、-NO 2、卤素、氨基、氰基、-R 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅，R 21取值如前所述。
R 6选自C 1-C 50亚烷基、C 3-C 12环亚烷基、C 2-C 12杂环亚烷基，其中，所述亚烷基、环亚烷基、杂环亚烷基中的H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅。
并且，R 4、R 5和R 6中碳原子数的总和小于等于50。
优选的，所述R 4和R 5独立的选自氢、C 1-C 40烷基，其中，所述烷基中的H原子可被-R 21、-OR 21、-COOR 21或-COR 21取代。
优选的，所述R 6选自C 1-C 40亚烷基，其中，所述亚烷基中的H原子可被-R 21、-OR 21、-COOR 21或-COR 21取代。
优选的，所述的R 4、R 5和R 6中碳原子数的总和小于等于40。
S 1选自-CH 2-、-CO-或-NR 24-；
S 2选自N或C；
S 3选自-O-、-CH 2-、-CO-或-NR 24-；
R 24选自氢、C 1-C 50烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中的H原子可被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代；所述的杂环中的杂原子可以是氧、氮、硫、磷或硅；
w选自1-20之间的整数，z选自2-20之间的整数。
优选的，S 1选自-CH 2-、-CO-；
S 2选自N；
S 3选自-O-、-CH 2-、-CO-；
w选自1-7之间的整数，z选自2-5之间的整数。
U选自R 24或
Figure PCTCN2020092974-appb-000009
其中U的结构式为
Figure PCTCN2020092974-appb-000010
时，结构式中的U为可重复单元，S 2连接下一个U基团；
g选自0-20之间的整数，h选自1-20之间的整数，
V选自
Figure PCTCN2020092974-appb-000011
其中，Q 2和T的取值如前所述。
R 12、R 13是聚合物的封端基团，所述R 12、R 13可以相同或不同，独立的选自氢、未经取代或任意H原子被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21、-COR 21或C 1-C 10烷基取代的C 4-C 30烷基、未经取代或任意H原子被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21、-COR 21或或C 1-30烷基基团取代的苯基、未经取代或苯基任意H原子被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21、-COR 21或C 1-30烷 基基团取代的C 7-9苯基烷基
Figure PCTCN2020092974-appb-000012
其中，R 7、R 8的取值如前所述。
优选的，所述R 12、R 13独立的选自氢，未经取代或任意H原子被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21、-COR 21或C 1-C 10烷基取代的C 4-C 30烷基，被两个-NR 7R 8取代的均三嗪基。
最优选的，所述R 12、R 13独立的选自氢，未经取代或任意H原子被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21、-COR 21或C 1-C 10烷基取代的C 4-C 30烷基。
在本发明的优选实施方式中，所述A 1、A 2、A 3、A 4、A 5、A 6……A n选自如下结构式：
Figure PCTCN2020092974-appb-000013
Figure PCTCN2020092974-appb-000014
在本发明中，≥4个C原子的碳链在催化剂作用下生成活化点，与哌啶环相连的O发生反应。如上所示，当单体有2个聚合位点时，形成线性聚合物，当单体有3个聚合位点时，3个位点均可以聚合，形成超支化聚合物。本发明所述的超支化聚合物时由AB X(X＝2)型单体缩聚反应生成的高度支化的聚合物，这种聚合物不是完美的树枝状大分子，是一种以特定聚合形式聚合的聚合物，称为超支化聚合物。A、B分别是具有连接作用的功能基团。如非专利文献“Flory,P.J.J.Am,Chem.Soc.1952,74,2718.”所述，超支化聚合物的概念在19世纪末就被提出，至今仍在被广泛研究。
因此，在本发明的优选实施方式中，所述通式Ⅰ的聚合型高分子空间位阻胺可以选自如下聚合形式：
Figure PCTCN2020092974-appb-000015
Figure PCTCN2020092974-appb-000016
Figure PCTCN2020092974-appb-000017
其中，
Figure PCTCN2020092974-appb-000018
代表可聚合位点，且
Figure PCTCN2020092974-appb-000019
位点可以与
Figure PCTCN2020092974-appb-000020
位点聚合，当聚合物中聚合为AB时，形成线性聚合物，简单表示为A-B-A-B；当聚合物中聚合为AB 2时，形成超支化聚合物，简单表示为如右的结构
Figure PCTCN2020092974-appb-000021
或者，在本发明的优选实施方式中，所述通式Ⅰ的聚合型高分子空间位阻胺还可以选自如下聚合形式：
Figure PCTCN2020092974-appb-000022
Figure PCTCN2020092974-appb-000023
上述聚合形式中，m n表示聚合物各单体的聚合度，可相同或不同，m n为1-20之间的整数。
优选的，R 1、R 2独立的选自氢或C 1-C 40烷基；R 3选自C 1-C 40亚烷基；R 1、R 2和R 3中碳原子数的总和小于等于40。
R 22选自C 1-C 5烷基。
R 7、R 8独立的选自C 1-C 10亚烷基，或者R 7、R 8与R 7和R 8之间的N原子形成C 3-C 10环亚烷基和C 2-C 8含氧环亚烷基。
R 4、R 5独立的选自氢或C 1-C 40烷基；R 6选自C 1-C 40亚烷基；R 4、R 5和R 6中碳原子数的总和小于等于40。
Q 1、Q 2独立的选自-CO-O-、-CO-NR 22-或-NR 22-，R 22选自C 1-C 5烷基。
本发明中，所述的烷基一词包含在给定的范围内的碳原子，例如，甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、2-乙基丁基、正戊基、异戊基、1-甲基戊基、1,3-二甲基丁基、正己基、1-甲基己基、正庚基、异庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、壬基、癸基、十一烷基、1-甲基十一烷基、十二烷基、1,1,3,3,5,5-六甲基己基。
烯基的实例是在给定的碳原子范围内的乙烯基、烯丙基以及丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基和十二碳烯基的支化和直链的异构体，烯 基一词也包括具有一个以上的共轭或非共轭双键的基团，例如可以含一个双键。
环烷基的一些实例是环丙基、环丁基、甲基环丁基、环戊基、甲基环戊基、二甲基环戊基、三甲基环戊基、乙基环戊基、丙基环戊基、异丙基环戊基、环己基、甲基环己基、二甲基环己基、乙基环己基、环庚基、甲基环庚基、环辛基。
杂环烷基的实例是含有N、O、S、Si等元素的环烷基。
亚烷基的实例是在给定的碳原子范围内的亚乙基、亚丙基、亚异丙基、亚丁基、亚仲丁基、亚异丁基、2-乙基亚丁基、亚戊基、亚异戊基、1-甲基亚戊基、1,3-二甲基亚丁基、亚己基、1-甲基亚己基、亚庚基、1,1,3,3-四甲基亚丁基、1-甲基亚庚基、3-甲基亚庚基、亚辛基、2-乙基亚己基、1,1,3-三甲基亚己基、1,1,3,3-四甲基亚戊基、亚壬基、亚癸基、亚十一烷基和亚十二烷基的支化和直链的异构体。
本发明所述的C 7-9苯基烷基，优选为苯甲基及2-苯乙基。
本发明所述的由1-3个C 1-4烷基取代的C 7-9苯基烷基，优选为甲基苯甲基、二甲基苯甲基、三甲基苯甲基或叔丁基苯甲基。
本发明提供一种通式Ⅰ的聚合型高分子空间位阻胺的制备方法，包括
将可聚合单体溶于溶剂或升温至熔融状态，依次加入催化剂和氢过氧化物，反应生成通式Ⅰ所述的聚合型高分子空间位阻胺，所述可聚合单体结构通式如下所示：
Figure PCTCN2020092974-appb-000024
Figure PCTCN2020092974-appb-000025
其中，
R和R’可以相同或不同，选自C 1-C 50烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中的H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅；并且，R和R’中碳原子数小于等于50；通式中其他参数的取值如前所述。
如上所示的可聚合单体是本领域已知的，部分有市售商品，或者可以按照本领域已知的方法合成。
本发明方法中使用的溶剂是芳香烃(如苯、二氯苯、氯苯等)、卤代烃、醇类(如甲醇、乙醇、乙二醇或甲醚)等常用有机溶剂或水。
优选的，所述的溶剂为苯、二氯苯、氯苯等芳香烃类溶剂。
本发明方法中反应温度为0-250℃，优选为25-100℃，更加优选的是45-150℃。
本发明方法中所使用的催化剂为金属化合物，其中金属化合物中的金属选自元素周期表中Ⅳb，Ⅴb，Ⅵb，Ⅶb和Ⅷ族金属元素。
优选的，所述的金属化合物选自乙酰丙酮氧钒、乙酰丙酮钒(三价)、羰基钴、氧化 铬(六价)、钛酸正丁酯、钛酸异丙酯、六羰基钼、三氧化钼、五氧化钒、三氧化铬和/或三氧化钨。
在本发明的优选实施方式中，所述的金属化合物为三氧化钼、五氧化钒、三氧化铬和/或三氧化钨。
本发明中催化剂的用量为0.0001-0.6摩尔当量，优选为0.01-0.3摩尔当量，更优选的是0.01-0.15摩尔当量，以可聚合单体的摩尔当量为基准。
本发明方法中所使用的氢过氧化物是无机氢过氧化物或有机氢过氧化物。
优选的，所述的无机氢过氧化物是H 2O 2；所述的有机氢过氧化物是烷基氢过氧化物和芳基氢过氧化物。
优选的，所述的烷基氢过氧化物为叔烷基氢过氧化物，如叔丁基过氧化氢、叔戊基过氧化氢、叔己基过氧化氢或叔辛基过氧化氢；所述的芳基氢过氧化物为乙苯氢过氧化物、过氧化四氢萘或异丙苯过氧化氢。
在本发明的优选实施方式中，所述的氢过氧化物选自H 2O 2、叔丁基过氧化氢或异丙苯过氧化氢。
本发明中氢过氧化物的用量为1-20摩尔当量，优选为1-10摩尔当量，更优选的是1-5摩尔当量，以可聚合单体的摩尔当量为基准。
本发明方法在惰性气氛如氮气、氦气或氩气等中进行，本发明方法可以在0.5-30巴，优选0.5-20巴，尤其是0.5-10巴，也可以在环境压力下进行。
本发明提供一种通式为Ⅰ的聚合型高分子空间位阻胺作为稳定剂和/或阻燃剂的用途。
优选的，通式为Ⅰ的聚合型高分子空间位阻胺对光、热或氧化敏感的有机物质具有稳定和/或阻燃的作用。
本发明提供一种组合物，所述组合物包括一种或两种以上对光、热或氧化敏感的有机物质和至少一种通式为Ⅰ的聚合型高分子空间位阻胺。
优选的，所述组合物还包括抗氧化剂、UV吸收剂、受阻胺光稳定剂、增强剂、填充剂、阻燃剂或其他添加剂中的一种或两种以上的组合。所述其他添加剂选自：塑化剂、润 滑剂、乳化剂、颜料、流变添加剂、催化剂、流动控制剂、光学增亮剂、耐火剂、抗静电剂及发泡剂。
优选的，所述组合物中，通式为Ⅰ的聚合型高分子空间位阻胺的量由有机物质的性质、最终用途及添加剂而定，通式为Ⅰ的聚合型高分子空间位阻胺可以各种比例使用。
优选的，所述通式为Ⅰ的聚合型高分子空间位阻胺的量为有机物质重量的0.01％-5％；
更优选的，所述通式为Ⅰ的聚合型高分子空间位阻胺的量为有机物质重量的0.05％-2％；
最优选的，所述通式为Ⅰ的聚合型高分子空间位阻胺的量为有机物质重量的0.05％-1％。
所述有机物质选自：聚烯烃、丙烯腈/丁二烯/苯乙烯、聚氯乙烯、聚甲基丙烯酸甲酯、聚缩醛、聚酰胺、聚酰亚胺、环氧树脂、聚氨酯、聚碳酸酯、聚氨酯、聚酯、聚砜、聚脲、聚苯乙烯、热塑性弹性体、乙烯-醋酸乙烯共聚物中的一种或两种以上的组合。
所述聚烯烃选自：含有基于乙烯和/或丙烯的橡胶相的聚乙烯或聚丙烯。所述的聚缩醛包括聚甲醛、含有环氧乙烷作为共聚单体的聚甲醛、用热塑性的聚氨酯、丙烯酸酯或MBS改性的聚缩醛。
所述聚酰胺包括由二胺及二院羧酸以及/或由氨基羧酸或相应的内酰胺衍生形成的聚酰胺和共聚酰胺，例如聚酰胺4、聚酰胺6、聚酰胺66、聚酰胺610、聚酰胺69、聚酰胺612、聚酰胺46、聚酰胺1212，聚酰胺11,、聚酰胺12，由间二甲苯二胺和己二酸得到的芳族聚酰胺；由六亚甲基和间苯二甲酸或/和对苯二甲酸在有或没有作为改性剂的弹性体存在下得到的聚酰胺。
所述的聚酯包括由二元羧酸和二醇以及/或从羟基羧酸或其对应的内酯衍生的聚酯，例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚1,4-二羟甲基环己烷对苯二甲酸酯和聚羟基苯甲酸酯，以及由羟基结尾的聚醚衍生物的嵌段共聚醚酯，和用聚碳酸酯或MBS改性的聚酯。
所述的热塑性弹性体包括聚烯烃热塑性弹性体及嵌段共聚物型聚苯乙烯热塑性弹性 体。聚烯烃热塑性弹性体包含聚烯烃树脂(如充当硬链段的聚乙烯及聚丙烯)及橡胶组合物(如充当软链段的乙烯-丙烯-二烯弹性体(EPDM))。嵌段共聚物型聚苯乙烯热塑性弹性体包含充当硬链段的聚苯乙烯及充当软链段的聚二烯(如聚丁二烯或聚异戊二烯)。或者，聚烯烃弹性体及聚苯乙烯弹性体的掺合物亦可用作本发明的热塑性弹性体。用于将软链段及硬链段组合于热塑性弹性体中的方法可大致分为简单掺和、通过共聚进行植入及动态交联。聚苯乙烯热塑性弹性体链段的组合包括SBS、SIS、SEBS、SEPS、这四种共聚物中任一种的氢化聚合物、SBR的氢化聚合物(HSBR)及聚丙烯与选自这些聚合物的一个或多个任意成员的掺合物。
所述抗氧化剂选自：酚和/或胺类抗氧剂、亚磷酸酯、硫代酯等。优选抗氧剂1010、抗氧剂1076、抗氧剂1098、抗氧剂168等。
所述UV吸收剂选自：水杨酸酯类、苯甲酸酯类、二苯甲酮类、笨并三唑类、三嗪类紫外线吸收剂。
所述受阻胺光稳定剂选自：与本发明化合物或其混合物具有不同结构的受阻胺光稳定剂，如双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、丁二酸与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合体、Chimassorb 944、Chimassorb 2020、UV-3346、UV-3529、Tinuvin 770、Tinuvin622LD、Tinuvin 292、
Figure PCTCN2020092974-appb-000026
HS-625、
Figure PCTCN2020092974-appb-000027
HS-950等受阻胺类光稳定剂。
所述填充剂及增强剂选自：碳酸钙、硅酸盐、玻璃纤维、玻璃珠、石棉、滑石、高岭土、云母、硫酸钡、金属氧化物及氢氧化物、碳黑、石墨、木粉及面粉或其他天然产物纤维、合成纤维。
本发明提供一种所述组合物在制备任何高分子材料制品中的应用，所述高分子材料如塑料、涂料、粘合剂等，选自：汽车内部或外部装饰材料、浮动装置、道路交通装置、农业制品、电器、家具、鞋类、卫生制品、保健制品领域。
所述的塑料产品可以通过本领域普通技术人员知晓的任何方法制造，包括但不限于挤出、挤出吹塑、薄膜流延、压延、注塑、吹塑、压塑、热成型、旋压成型、吹挤和旋转铸 塑。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明的部分实施例，而不是全部。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将81g 2,2,6,6-四甲基-4-哌啶十二胺和2g三氧化钼溶于400mL氯苯中，加热至120℃，然后缓慢滴加60g叔丁基氢过氧化物(70％水溶液)，持续搅拌12h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到60g的目标产品。
分子量：1650(Mn)
动态粘度(140℃)：152mPas
实施例2
将81g 2,2,6,6-四甲基-4-哌啶十二胺和1g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加35g叔丁基氢过氧化物(70％水溶液)，持续搅拌48h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到70g的目标产品。
分子量：1850(Mn)
动态粘度(140℃)：178mPas
实施例3
将81g 2,2,6,6-四甲基-4-哌啶十二胺和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到75g的目标产品。
分子量：2028(Mn)
动态粘度(140℃)：232mPas
实施例4
将85g N-十二烷基-2,2,6,6-四甲基哌嗪酮和3g三氧化钼溶于400mL氯苯中，加热至 140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到77g的目标产品。
分子量：1950(Mn)
动态粘度(140℃)：241mPas
实施例5
将106g 2,2,6,6-四甲基-4-哌啶基硬脂酸酯和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到90g的目标产品。
分子量：2080(Mn)
动态粘度(140℃)：267mPas
实施例6
(1)将36.9g三聚氯氰溶于300mL二甲苯中，冷至10℃后，加入42.4g N-(2,2,6,6-四甲基-4-哌啶基)正丁胺(三聚氯氰与N-(2,2,6,6-四甲基-4-哌啶基)正丁胺的摩尔比为1:1)搅拌1h，接着加入37g十二烷基胺(三聚氯氰与十二烷基胺的摩尔比为1:1)，于60℃搅拌3h，然后加入50g氢氧化钠水溶液(30％)，搅拌3h，分相，最后加入17.5g吗啉(三聚氯氰与吗啉的摩尔比为1:1)，升温至110℃，继续搅拌6h。完全反应后，进行相分离且用水将有机相洗涤若干次，随后将有机相分离并减压浓缩，得到116.1g中间体1。
Figure PCTCN2020092974-appb-000028
(2)将86g中间体1和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到72g目标产品。
分子量：1800(Mn)
动态粘度(140℃)：532mPas
实施例7
(1)将36.9g三聚氯氰溶于300mL二甲苯中，冷至10℃后，加入42.4g N-(2,2,6,6-四甲基-4-哌啶基)正丁胺(三聚氯氰与N-(2,2,6,6-四甲基-4-哌啶基)正丁胺的摩尔比为1:1)搅拌1h，然后加入50g氢氧化钠水溶液(30％)，搅拌3h，分相，然后加入74g十二烷基胺(三聚氯氰与十二烷基胺的摩尔比为1:2)，升温至100℃，继续搅拌6h。完全反应后，进行相分离且用水将有机相洗涤若干次，随后将有机相分离并减压浓缩，得到134g中间体2。
Figure PCTCN2020092974-appb-000029
(2)将98g中间体2和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到85g目标产品。
分子量：1863(Mn)
动态粘度(140℃)：650mPas
实施例8
(1)将36.9g三聚氯氰溶于300mL二甲苯中，冷至20℃后，加入84.8g N-(2,2,6,6-四甲基-4-哌啶基)正丁胺(三聚氯氰与N-(2,2,6,6-四甲基-4-哌啶基)正丁胺的摩尔比为1:2)搅拌1h，加入50g氢氧化钠水溶液(30％)，搅拌3h，分相，然后加入37g十二烷基胺(三聚氯氰与十二烷基胺的摩尔比为1:1)，升温至110℃，继续搅拌6h。完全反应后，进行相分离且用水将有机相洗涤若干次，随后将有机相分离并减压浓缩，得到140.2g中间体3。
Figure PCTCN2020092974-appb-000030
(2)将102.6g中间体3和3g三氧化钼溶于400mL氯苯中，加热至120℃，然后缓慢滴加60g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到95g目标产品。
分子量：1950(Mn)
动态粘度(140℃)：693mPas
实施例9
将88g 2,2,4,4-四甲基-4-哌啶基十二烷基酰胺和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到75g的目标产品。
分子量：1873(Mn)
动态粘度(140℃)：337mPas
实施例10
将150.5g 2,2,4,4-四甲基-20-月桂基氧基羰乙基-7-氧杂-3,20-三氮杂二螺[5.1.11.2]21烷-21-酮和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到135.7g的目标产品。
分子量：1815(Mn)
动态粘度(140℃)：527mPas
实施例11
将90.5g 2,2,4,4-四甲基-7-氧杂-3,20-三氮杂二螺[5.1.11.2]21烷-21-酮和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到78g的目标产品。
分子量：1835(Mn)
动态粘度(140℃)：417mPas
实施例12
将101.5g 3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到90g的目标产品。
分子量：1932(Mn)
动态粘度(140℃)：384mPas
实施例13
将32.4g 2,2,6,6-四甲基-4-哌啶十二胺、42.3g 2,2,6,6-四甲基-4-哌啶基硬脂酸酯和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到67g的目标产品。
分子量：2054(Mn)
动态粘度(140℃)：243mPas
实施例14
将57.5g中间体1、68.4g中间体3和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到108g的目标产品。
分子量：2628(Mn)
动态粘度(140℃)：983mPas
实施例15
将32.4g 2,2,6,6-四甲基-4-哌啶十二胺、42.3g 2,2,6,6-四甲基-4-哌啶基硬脂酸酯、57.5g中间体1和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到110g的目标产品。
分子量：2207(Mn)
动态粘度(140℃)：413mPas
实施例16
将81g 2,2,6,6-四甲基-4-哌啶十二胺和3g三氧化钼溶于400mL氯苯中，加热至140℃，然后缓慢滴加50g叔丁基氢过氧化物(70％水溶液)，持续搅拌60h。完全反应后，加入过量的饱和的亚硫酸钠溶液，搅拌，分相，过滤，有机相浓缩得到75g的中间体4。
将60g中间体4和32.3g二正丁胺溶于400mL氯苯中，加热至140℃，持续搅拌6h。反应结束后，有机相浓缩得到85g的目标产品
分子量：2286(Mn)
动态粘度(140℃)：271mPas
实施例17稳定聚丙烯材料实验
基础配方：
标准聚合物：79.8wt％热塑性聚丙烯；20wt％水滑石；0.20wt％抗氧剂(AO-1010)；
1#为100wt％标准聚合物；
2#为99.7wt％标准聚合物，0.3wt％空间位阻胺(实施例3)；
3#为99.7wt％标准聚合物，0.3wt％空间位阻胺(实施例5)；
4#为99.7wt％标准聚合物，0.3wt％空间位阻胺(实施例6)；
5#为99.7wt％标准聚合物，0.3wt％空间位阻胺(实施例8)；
6#为99.7wt％标准聚合物，0.3wt％空间位阻胺(实施例13)；
7#为99.7wt％标准聚合物，0.4wt％空间位阻胺(实施例14)；
8#为99.7wt％标准聚合物，0.3wt％空间位阻胺(实施例15)；
制备测试样品：
在混合机中预先混合各组分，然后220℃下双螺杆挤出机上进行挤出、造粒。在80℃下干燥8h，然后在240℃下使用注塑机注塑成型。最后将样品按照SAE J 2527标准进行氙灯老化测试，测试结果如表1所示：
表1氙灯老化后样品的△E*(低值为所需)
Figure PCTCN2020092974-appb-000031
实施例18稳定热塑性聚乙烯试验
基础配方：
标准聚合物：79.8wt％热塑性聚乙烯；20wt％碳酸钙；0.20wt％抗氧剂(AO-1010)；
1#为100wt％标准聚合物；
2#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例3)；
3#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例5)；
4#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例6)；
5#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例8)；
6#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例13)；
7#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例14)；
8#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例15)；
制备测试样品：
在混合机中预先混合各组分，然后190℃下双螺杆挤出机上进行挤出、造粒。在80℃下干燥8h，然后在200℃下使用吹膜机吹塑成型。最后将样品按照GB/T 16422.2-2014标准进行人工氙灯加速老化测试，测试结果如表2所示：
表2拉伸强度保留率％
Figure PCTCN2020092974-appb-000032
实施例19稳定热塑性聚氯乙烯试验
基础配方：
标准聚合物：
65.5wt％热塑性聚氯乙烯；31.5wt％塑化剂；1.6wt％环氧大豆油；1.4wt％钙锌稳定剂；
1#为100wt％标准聚合物；
2#为99.5wt％标准聚合物，0.25wt％UV-531；0.25wt％空间位阻胺(实施例3)；
3#为99.5wt％标准聚合物，0.25wt％UV-531；0.25wt％空间位阻胺(实施例5)；
4#为99.5wt％标准聚合物，0.25wt％UV-531；0.25wt％空间位阻胺(实施例6)；
5#为99.5wt％标准聚合物，0.25wt％UV-531；0.25wt％空间位阻胺(实施例8)；
制备测试样品：
在混合机中华预先混合各组分，随后在165℃下双辊研磨机上混炼7分钟，得到所需样品。最后将样品按照GB/T 16422.2-2014标准进行氙灯老化测试，测试结果如表3所示：
表3断裂伸长率保留率％
Figure PCTCN2020092974-appb-000033
实施例20稳定热塑性聚酰胺6试验
基础配方：
标准聚合物：79.8wt％热塑性聚酰胺6；20wt％碳酸钙；0.20wt％抗氧剂(AO-1098)；
1#为100wt％标准聚合物；
2#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例3)；
3#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例9)；
4#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例10)；
5#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例11)；
6#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例12)；
制备测试样品：
在混合机中预先混合各组分，然后260℃下双螺杆挤出机上进行挤出、造粒，在80℃下干燥12h，然后在265℃下使用注塑机注塑成型。最后将样品按照标准GB/T16422.2-2014进行氙灯老化测试，测试结果如表4所示：
表4氙灯老化后样品的△E*(低值为所需)
Figure PCTCN2020092974-appb-000034
实施例21在PP薄膜中作为阻燃剂的性能测试
基础配方：
标准聚合物：99.65wt％热塑性聚丙烯；0.05wt％硬脂酸钙；0.30wt％抗氧剂(AO-1010：AO-168＝1:1)；
1#为100wt％标准聚合物；
2#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例3)；
3#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例5)；
4#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例6)；
5#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例8)；
制备测试样品：
在混合机中预先混合各组分，然后220℃下双螺杆挤出机上进行挤出、造粒。在80℃下干燥8h，然后在热压机中压塑制备。最后将样品按照DIN 4102-B2标准进行样品的阻燃性测试，测试结果如表5所示：
表5样品阻燃性能
样品 重量损失/％ 燃烧长度/mm 燃烧滴液 合格/不合格
1# 100 190 是 不合格
2# 8.5 104 是 合格
3# 8.4 102 是 合格
4# 8.7 105 是 合格
5# 6.5 87 是 合格
实施例22在聚酰胺6中作为阻燃剂的性能测试
基础配方：标准聚合物：79.8wt％热塑性聚酰胺6；20wt％碳酸钙；0.20wt％抗氧剂(AO-1098)；
1#为100wt％标准聚合物；
2#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例3)；
3#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例9)；
4#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例10)；
5#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例11)；
6#为99.6wt％标准聚合物，0.4wt％空间位阻胺(实施例12)；
制备测试样品：
在混合机中预先混合各组分，然后260℃下双螺杆挤出机上进行挤出、造粒在80℃下干燥12h，然后在265℃下使用注塑机注塑成型。最后将样品按照UL94标准进行样品的阻燃性测试，测试结果如表6所示：
表6样品阻燃性能
样品 V级 燃烧滴液
1# 2 是
2# 2 是
3# 1 否
4# 1 否
5# 1 否
6# 1 否
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种聚合型高分子空间位阻胺，其通式Ⅰ如下：
    Figure PCTCN2020092974-appb-100001
    其中，m n为1-20之间的整数；n为1-20之间的整数；
    A 1、A 2、A 3、A 4、A 5、A 6……A n可以相同也可以不同，所述A 1、A 2、A 3、A 4、A 5、A 6……A n结构独立的选自通式Ⅱ，Ⅲ、Ⅳ或Ⅴ；
    Figure PCTCN2020092974-appb-100002
    其中，G 1与G 2可以相同或不同，独立的选自C 1-C 18烷基、C 2-C 18烯基、C 2-C 18炔基、苯基、C 3-C 12环烷基或C 2-C 12杂环烷基；或者G 1、G 2与G 1和G 2之间的碳原子形成C 3-C 12环烷基，其中烷基、烯基、炔基、苯基、环烷基或杂环烷基上任意氢原子可以被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅；
    所述的R 21选自氢、未经取代或任意氢原子被C 1-C 18烷基取代的C 1-C 40烷基；未经取代或任意氢原子被1-3个-OH或C 1-30烷基基团取代的苯基、未经取代或苯基任意氢原子被1-3个-OH和C 1-30烷基基团取代的C 7-9苯基烷基；
    E选自-CO-、或-(CH 2) a-，a选自0、1、或2；
    R 1与R 2可以相同或不同，独立的选自氢、C 1-C 50烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中的H原子可被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子可以是氧、氮、硫、磷或硅；
    R 3选自C 1-C 50亚烷基、C 3-C 12环亚烷基、C 2-C 12杂环亚烷基，其中，所述亚烷基、环亚烷基、杂环亚烷基中的H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述的杂环中的杂原子选自氧、氮、硫、磷或硅；
    并且，R 1、R 2和R 3中碳原子数的总和小于等于50；
    Q 1与Q 2可以相同或不同，独立的选自-O-、-O-CO-O-、-CO-O-、-CO-NR 22-、-NR 22-、-NR 22-CO-NR 23-或-(CH 2) b-，b是0、1、或2；
    其中，所述的R 22、R 23独立的选自氢、未经取代或任意氢原子被C 1-C 18烷基取代的C 1-C 40烷基；未经取代或任意氢原子被1-3个-OH或C 1-30烷基基团取代的苯基、未经取代或苯基被1-3个-OH和C 1-30烷基基团取代的C 7-9苯基烷基；
    T的结构式选自未经取代或任意H原子被C 1-C 5烷基取代的C 1-C 10亚烷基、
    Figure PCTCN2020092974-appb-100003
    m p为1-20之间的整数；
    R 7、R 8可以相同或不同，选自氢、C 1-C 40烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代；或者R 7、R 8与R 7和R 8之间的N原子形成C 3-C 12环亚烷基、C 2-C 12杂环亚烷基，其中，所述环亚烷基、杂环亚烷基中H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代；所述的杂环中杂原子选自氧、氮、 硫、磷或硅；
    Q 3选自-O-、-O-CO-O-、-CO-O-、-CO-NR 22-、-NR 22-、NR 22-CO-NR 23-或-(CH 2) b-，b是0、1、或2；
    R 4、R 5可以相同或不同，独立的选自氢、C 1-C 50烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中的H原子可被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述杂环中杂原子选自氧、氮、硫、磷或硅；
    R 6选自C 1-C 50亚烷基、C 3-C 12环亚烷基、C 2-C 12杂环亚烷基，其中，所述亚烷基、环亚烷基、杂环亚烷基中的H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述杂环中杂原子选自氧、氮、硫、磷或硅；
    并且，R 4、R 5和R 6中碳原子数的总和小于等于50；
    S 1选自-CH 2-、-CO-或-NR 24-；
    S 2选自N或C；
    S 3选自-O-、-CH 2-、-CO-或-NR 24-；
    R 24选自氢、C 1-C 50烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中的H原子可被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代；所述杂环中杂原子选自氧、氮、硫、磷、硅或卤素；
    w选自1-20之间的整数，z选自2-20之间的整数；
    U选自R 24或
    Figure PCTCN2020092974-appb-100004
    g选自0-20之间的整数，h选自1-20之间的整数，
    V选自
    Figure PCTCN2020092974-appb-100005
    R 12、R 13是聚合物的封端基团，所述R 12、R 13可以相同或不同，独立的选自氢、未经 取代或任意H原子被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21、-COR 21或C 1-C 10烷基取代的C 4-C 30烷基、未经取代或任意H原子被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21、-COR 21或C 1-30烷基基团取代的苯基、未经取代或苯基任意H原子被羟基、-NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21、-COR 21或C 1-30烷基基团取代的C 7-9苯基烷基、
    Figure PCTCN2020092974-appb-100006
  2. 根据权利要求1所述的聚合型高分子空间位阻胺，其特征在于，G 1、G 2独立的选自C 1-C 4烷基；所述的R 21选自C 1-C 20烷基；E选自-CO-、或-CH 2-；所述的Q 1、Q 2独立的选自-O-、-CO-O-、-CO-NR 22-或-NR 22-；所述的R 22、R 23独立的选自氢、C 1-C 20烷基。
  3. 根据权利要求2所述的聚合型高分子空间位阻胺，其特征在于，G 1、G 2独立的选自甲基，所述A 1、A 2、A 3、A 4、A 5、A 6……A n选自如下结构式：
    Figure PCTCN2020092974-appb-100007
    Figure PCTCN2020092974-appb-100008
    其中，当单体有2个聚合位点时，形成线性聚合物，当单体有3个聚合位点时，形成超支化聚合物。
  4. 根据权利要求3所述的聚合型高分子空间位阻胺，其特征在于，所述R 1和R 2独立的选自氢、C 1-C 40烷基，其中，所述烷基中的H原子可被-R 21、-OR 21、-COOR 21或-COR 21取代；所述R 3选自C 1-C 40亚烷基，其中，所述亚烷基中的H原子可被-R 21、-OR 21、-COOR 21或-COR 21取代；所述的R 1、R 2和R 3中碳原子数的总和小于等于40；
    所述的R 7和R 8独立的选自氢、未经取代或被-R 21取代的C 1-C 20烷基；或者R 7、R 8与R 7和R 8之间的N原子形成未经取代的C 3-C 12环亚烷基或C 2-C 12杂环亚烷基；
    优选的，所述的C 2-C 12杂环亚烷基优选为C 2-C 12含氧杂环亚烷基；
    所述的Q 3选自-O-、-CO-O-、-CO-NR 22-或-NR 22-；
    所述R 4和R 5独立的选自氢、C 1-C 40烷基，其中，所述烷基中的H原子可被-R 21、-OR 21、-COOR 21或-COR 21取代；所述R 6选自C 1-C 40亚烷基，其中，所述亚烷基中的H原子可被-R 21、-OR 21、-COOR 21或-COR 21取代；所述的R 4、R 5和R 6中碳原子数的总和小于等于40。
  5. 根据权利要求4所述的聚合型高分子空间位阻胺，其特征在于，所述的R 21选自氢或C 1-C 12烷基；
    Q 1、Q 2独立的选自-CO-O-、-CO-NR 22-或-NR 22-；
    所述的R 22、R 23独立的选自氢、C 1-C 12烷基；
    所述的R 7和R 8独立的选自未经取代的C 1-C 20烷基；或者R 7、R 8与R 7和R 8之间的N原子形成未经取代的C 3-C 10环亚烷基或C 2-C 8含氧环亚烷基；
    Q 3选自-NR 22-。
  6. 根据权利要求1-5任一所述的聚合型高分子空间位阻胺，其特征在于，所述通式Ⅰ的聚合型高分子空间位阻胺可以选自如下聚合形式：
    Figure PCTCN2020092974-appb-100009
    Figure PCTCN2020092974-appb-100010
    Figure PCTCN2020092974-appb-100011
    其中，
    Figure PCTCN2020092974-appb-100012
    代表可聚合位点，且
    Figure PCTCN2020092974-appb-100013
    位点可以与
    Figure PCTCN2020092974-appb-100014
    位点聚合，当聚合物中聚合为AB时，形成线性聚合物；当聚合物中聚合为AB 2时，形成超支化聚合物；
    m n为1-20之间的整数；
    R 1、R 2独立的选自氢或C 1-C 40烷基；R 3选自C 1-C 40亚烷基；R 1、R 2和R 3中碳原子数的总和小于等于40；
    R 22选自C 1-C 5烷基；
    R 7、R 8独立的选自C 1-C 10亚烷基，或者R 7、R 8与R 7和R 8之间的N原子形成C 3-C 10环亚烷基和C 2-C 8含氧环亚烷基；
    R 4、R 5独立的选自氢或C 1-C 40烷基；R 6选自C 1-C 40亚烷基；R 4、R 5和R 6中碳原子数的总和小于等于40；
    Q 1、Q 2、Q 3独立的选自-CO-O-、-CO-NR 22-或-NR 22-，R 22选自C 1-C 5烷基。
  7. 一种权利要求1所述的通式Ⅰ的聚合型高分子空间位阻胺的制备方法，包括将可聚合单体溶于溶剂或升温至熔融状态，依次加入催化剂和氢过氧化物，反应生成通式Ⅰ所述的聚合型高分子空间位阻胺，所述可聚合单体结构通式如下所示：
    Figure PCTCN2020092974-appb-100015
    Figure PCTCN2020092974-appb-100016
    或者
    Figure PCTCN2020092974-appb-100017
    其中，
    R和R’可以相同或不同，选自C 1-C 50烷基、C 3-C 12环烷基、C 2-C 12杂环烷基，其中，所述烷基、环烷基、杂环烷基中的H原子可被羟基、NO 2、卤素、氨基、氰基、-R 21、-OR 21、-COOR 21或-COR 21取代，所述杂环中杂原子选自氧、氮、硫、磷或硅；并且，R和R’中碳原子数小于等于50；
    所述溶剂是二氯苯、氯苯、甲苯、卤代烃、甲醇、乙醇、乙二醇、甲醚或水；
    所述催化剂为金属化合物，其中金属化合物中的金属选自元素周期表中Ⅳb，Ⅴb，Ⅵb， Ⅶb和Ⅷ族金属元素，优选的，所述的金属化合物选自乙酰丙酮氧钒、乙酰丙酮钒(三价)、羰基钴、氧化铬(六价)、钛酸正丁酯、钛酸异丙酯、六羰基钼、三氧化钼、五氧化钒、三氧化铬和/或三氧化钨；
    所述氢过氧化物是无机氢过氧化物或有机氢过氧化物，所述的无机氢过氧化物是H 2O 2；所述的有机氢过氧化物是烷基氢过氧化物和芳基氢过氧化物。
  8. 一种权利要求1所述的通式为Ⅰ的聚合型高分子空间位阻胺作为稳定剂和/或阻燃剂的用途，优选的，通式为Ⅰ的聚合型高分子空间位阻胺对光、热或氧化敏感的有机物质具有稳定和/或阻燃的作用。
  9. 一种组合物，所述组合物包括一种或两种以上对光、热或氧化敏感的有机物质和至少一种通式为Ⅰ的聚合型高分子空间位阻胺，所述有机物质和通式为Ⅰ的聚合型高分子空间位阻胺可以各种比例使用。
  10. 一种权利要求9所述的组合物在制备任何高分子材料制品中的应用，所述高分子材料，如塑料、涂料、粘合剂等，选自：汽车内部或外部装饰材料、浮动装置、道路交通装置、农业制品、电器、家具、鞋类、卫生制品、保健制品领域。
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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR810E (fr) 1901-09-04 1903-04-02 Societe G. Et P. De Mestral Perfectionnements à l'arc électrique dans les lampes à arc
US4265805A (en) * 1980-04-01 1981-05-05 American Cyanamid Company Polymeric light stabilizers containing tetralkyl piperidine moieties
US5015678A (en) * 1989-03-21 1991-05-14 Ciba-Geigy Corporation Stabilizers derived from N-hydroxy hindered amines by Michael addition reactions
EP0782994A1 (en) 1995-12-04 1997-07-09 Ciba SC Holding AG Block oligomers containing 2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials
WO1999000450A1 (en) 1997-06-30 1999-01-07 Ciba Specialty Chemicals Holding Inc. Flame retardant compositions
CN1273241A (zh) * 1999-02-25 2000-11-15 西巴特殊化学品控股有限公司 羟基取代的n－烷氧基受阻胺
US6599963B2 (en) 1997-06-30 2003-07-29 Ciba Specialty Chemicals Corporation Flame retardant compositions
CN1753871A (zh) 2003-02-26 2006-03-29 西巴特殊化学品控股有限公司 水相容空间位阻烷氧基胺和羟基取代的烷氧基胺
CN101048378A (zh) 2004-11-02 2007-10-03 西巴特殊化学品控股有限公司 N－烷氧基胺的合成方法
CN101484423A (zh) 2006-07-05 2009-07-15 西巴控股有限公司 制备位阻硝酰基醚的方法
US20110160453A1 (en) 2006-07-05 2011-06-30 Abdel-Ilah Basbas Process for the preparation of sterically hindered nitroxyl ethers
CN102137889A (zh) * 2008-08-28 2011-07-27 巴斯夫欧洲公司 用于无生命有机材料的稳定剂
CN102307940A (zh) 2009-02-04 2012-01-04 巴斯夫欧洲公司 稳定剂
CN102702174A (zh) * 2012-06-19 2012-10-03 南通惠康国际企业有限公司 光稳定剂三(1-环己氧基-2,2,6,6-四甲基-4-氧基-哌啶基)-1,3,5-三嗪的制备方法
US8765848B2 (en) 2006-03-16 2014-07-01 Clariant Finance (Bvi) Limited Modified waxes, a process for their preparation, and their use
CN105636954A (zh) 2013-10-17 2016-06-01 巴斯夫欧洲公司 三嗪、哌啶和吡咯烷基受阻胺光稳定剂

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0309402B2 (en) * 1987-09-21 2002-06-12 Ciba Specialty Chemicals Holding Inc. N-substituted hindered amine stabilizers
EP0365481A1 (en) * 1988-10-19 1990-04-25 Ciba-Geigy Ag Polymeric substrates stabilized with N-substituted hindered amines
TW338768B (en) * 1994-06-02 1998-08-21 Ciba Sc Holding Ag Oligometic HALS phosphites and HALS phosphonites as stabilizers
ES2148469T3 (es) * 1994-11-15 2000-10-16 Moreno Paolini N-hidroxipiperidinas como agentes de barrido de radicales superoxido.
WO1998018830A1 (en) * 1996-10-31 1998-05-07 Ciba Specialty Chemicals Holding Inc. Functionalised polymers
SG74700A1 (en) * 1998-02-25 2000-08-22 Ciba Sc Holding Ag Preparation of sterically hindered amine ethers
JP4190093B2 (ja) * 1999-06-24 2008-12-03 株式会社Ａｄｅｋａ ピペリジン誘導体重合物及びこれを含有する高分子組成物
US6455616B1 (en) * 2000-03-07 2002-09-24 Union Carbide Chemicals & Plastics Technology Corporation Polyethylene crosslinkable composition
GB0005629D0 (en) * 2000-03-10 2000-05-03 Clariant Int Ltd Light stabilizer composition
ITTO20040124A1 (it) * 2004-03-01 2004-06-01 Medestea Internaz Srl Nuovi impieghi in terapia di derivati di n-piperidina particolarmente per il trattamento di patologie neurodegenerative
JP2007533867A (ja) * 2004-04-23 2007-11-22 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 可染性ポリオレフィン繊維及び布
CN101405306B (zh) * 2006-03-16 2011-07-27 克莱里安特财务(Bvi)有限公司 改性蜡、其制备方法及其用途
CN101381477B (zh) * 2008-10-15 2011-04-27 天津大学 新型受阻胺光稳定剂及其合成方法
CA2762361A1 (en) 2009-06-08 2010-12-16 Basf Se Novel sterically hindered amine light stabilizers
CN101591331B (zh) * 2009-06-25 2014-05-21 中国乐凯胶片集团公司 一种受阻胺光稳定剂的制备方法
JP5593784B2 (ja) 2010-03-30 2014-09-24 大日本印刷株式会社 積層体
CN104140556B (zh) * 2014-08-13 2017-01-18 北京天罡助剂有限责任公司 一种具有抗光氧化、抗热氧化性能的三嗪类化合物及其合成方法
CN105348525B (zh) * 2015-10-19 2017-10-27 北京天罡助剂有限责任公司 一种低碱性聚合型受阻胺光稳定剂及其制备方法
CN109134928B (zh) * 2018-10-31 2020-05-19 天集化工助剂（沧州）有限公司 N-取代的三嗪受阻胺光稳定剂及其制备方法和应用

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR810E (fr) 1901-09-04 1903-04-02 Societe G. Et P. De Mestral Perfectionnements à l'arc électrique dans les lampes à arc
US4265805A (en) * 1980-04-01 1981-05-05 American Cyanamid Company Polymeric light stabilizers containing tetralkyl piperidine moieties
US5015678A (en) * 1989-03-21 1991-05-14 Ciba-Geigy Corporation Stabilizers derived from N-hydroxy hindered amines by Michael addition reactions
EP0782994A1 (en) 1995-12-04 1997-07-09 Ciba SC Holding AG Block oligomers containing 2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials
WO1999000450A1 (en) 1997-06-30 1999-01-07 Ciba Specialty Chemicals Holding Inc. Flame retardant compositions
US6599963B2 (en) 1997-06-30 2003-07-29 Ciba Specialty Chemicals Corporation Flame retardant compositions
CN1273241A (zh) * 1999-02-25 2000-11-15 西巴特殊化学品控股有限公司 羟基取代的n－烷氧基受阻胺
CN1753871A (zh) 2003-02-26 2006-03-29 西巴特殊化学品控股有限公司 水相容空间位阻烷氧基胺和羟基取代的烷氧基胺
CN101048378A (zh) 2004-11-02 2007-10-03 西巴特殊化学品控股有限公司 N－烷氧基胺的合成方法
US8765848B2 (en) 2006-03-16 2014-07-01 Clariant Finance (Bvi) Limited Modified waxes, a process for their preparation, and their use
CN101484423A (zh) 2006-07-05 2009-07-15 西巴控股有限公司 制备位阻硝酰基醚的方法
US20110160453A1 (en) 2006-07-05 2011-06-30 Abdel-Ilah Basbas Process for the preparation of sterically hindered nitroxyl ethers
CN102137889A (zh) * 2008-08-28 2011-07-27 巴斯夫欧洲公司 用于无生命有机材料的稳定剂
CN102307940A (zh) 2009-02-04 2012-01-04 巴斯夫欧洲公司 稳定剂
CN102702174A (zh) * 2012-06-19 2012-10-03 南通惠康国际企业有限公司 光稳定剂三(1-环己氧基-2,2,6,6-四甲基-4-氧基-哌啶基)-1,3,5-三嗪的制备方法
CN105636954A (zh) 2013-10-17 2016-06-01 巴斯夫欧洲公司 三嗪、哌啶和吡咯烷基受阻胺光稳定剂

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FLORY, P. J., J. AM, CHEM. SOC., vol. 74, 1952, pages 2718
ROY, RAJ KUMAR ET AL.: "Convergent Synthesis of Digitally-encoded Poly (alkoxyamine amide)s", CHEM. COMMUN., vol. 51, 31 December 2015 (2015-12-31), XP055773227, DOI: 15677-15680 *
See also references of EP3992230A4

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