CN104744726A - Stabilizing agent for improving organic material weatherability and stabilizing agent-modified polymer - Google Patents
Stabilizing agent for improving organic material weatherability and stabilizing agent-modified polymer Download PDFInfo
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- CN104744726A CN104744726A CN201310740562.5A CN201310740562A CN104744726A CN 104744726 A CN104744726 A CN 104744726A CN 201310740562 A CN201310740562 A CN 201310740562A CN 104744726 A CN104744726 A CN 104744726A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
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Abstract
The invention discloses a stabilizing agent for improving organic material weatherability. The stabilizing agent comprises a difunctional compound shown in the formula (IV), and in the formula (IV), R1 represents C1-C8 alkyl, R2 represents C1-C18 alkylene, cycloalkylene, arylidene, aralkylene or alkarylene, X represents -NH-NH- or a group shown in the following description, Y1 and Y2 are the same or differently represent -O- or -NH-, R represents C1-C6 alkylene and n is in a range of 0-2. The invention also provides a stabilizing agent-modified polymer. The stabilizing agent-modified polymer comprises an organic polymer base material and the stabilizing agent. The stabilizing agent can substantially improve yellow stain resistance of the organic polymer material in different environments.
Description
Technical field
The present invention relates to a kind of stablizer for promoting organic materials weathering resistance, particularly relating to the stablizer that one comprises the hindered phenol compound with amine urea (semicarbazide) structure.
Background technology
General organic polymer material (such as plastics, resin, makeup, colorant, coating, textiles) is easily subject to light, heat, acid, alkali or oxynitride (NO
x) destroyed, and then cause look to become or material breakdown.If applicable organic additive (such as antioxidant or photostabilizer) can be added in organic polymer material, above-mentioned materials can be protected to reduce damage.Such as, if add the chemical substance of tool resistance of oxidation or tool ultraviolet absorption characteristic, can absorb or change the energy of UV-light, and then keep the gloss of material, and improve the weather resistance of material.
Industrial generally employing above-mentionedly adds additivated mode to promote the anti-oxidation characteristics of organic polymer material at present, and described additive belongs to hindered phenol type antioxidant or phosphorous organic oxidation-resistant agent mostly.Such as TaiWan, China patent discloses No. 201229214, No. 20120252931st, U.S. Patent Publication etc. is all to strengthen resistance of oxidation with hindered phenol type antioxidant.Although these hindered phenol type antioxidants can improve the resistance of oxidation of organic polymer material when high temperature process or heat are dried, for improving its room temperature yellowing resistance (anti-NO
x) and alkali resistance then effect be not clearly.
Summary of the invention
The object of the present invention is to provide a kind of stablizer, the color inhibition effect of organic polymer under various varying environment can be promoted.The present invention, for promoting the stablizer of organic materials weathering resistance, comprises: following difunctional compound shown in formula IV:
In formula IV, R
1represent C
1to C
8alkyl; R
2represent C
1to C
18alkylidene group, cycloalkylidene, arylidene, sub-aralkyl or alkarylene; And X represent-NH-NH-or
y
1and Y
2represent-O-or-NH-identical or differently; R represents C
1to C
6alkylidene group; And n represents 0 to 2.
Another object of the present invention, is to provide a kind of polymkeric substance through modification, includes organic polymer base material, and stablizer as above.
Beneficial effect of the present invention is: the difunctional compound in stablizer of the present invention contributes to promoting the color inhibition effect of organic polymer under various varying environment, and can use with other additive.
embodiment
Below in conjunction with embodiment, the present invention is described in detail:
Preferably, in formula IV, R
2represent C
6to C
18alkylidene group or alkarylene.More preferably, R
2represent
Preferably, in formula IV, X represents-NH-NH-and R
1represent the tertiary butyl.
Preferably, in formula IV, R represents ethylidene.
Preferably, described difunctional compound is obtained by hindered phenol compound, polyisocyanates and the hydrazine reaction shown in following formula I:
In the present invention, the hindered phenol compound as above shown in formula I obtains by carrying out monolateral condensation separating methanol to react under the existence having catalyzer or catalyst-free as shown in the formula the methyl compound shown in (I ') and H-X-H:
Preferably, described catalyzer is optional from organo-tin compound, sodium methylate, organic bases or mineral alkali.
Preferably, H-X-H is selected from hydrazine hydrate (H
2n-NH
2h
2o), thanomin (H
2nCH
2cH
2or triglycol (HO-C OH)
2h
4oC
2h
4oC
2h
4-OH).
Preferably, described polyisocyanates is shown in following formula II:
OCN-R
2-NCO (Ⅱ)。
In the present invention, as above the polyisocyanates shown in formula II can be selected from PPDI (1, 4-phenylene diisocyanate), tolylene diisocyanate (tolylene diisocyanate), isophorone diisocyanate (isophorone diisocyanate, IPDI), methylene-bis (4-cyclohexyl diisocyanate) [methylene-bis (4-cyclohexyl isocyanate)], 1, 6-hexamethylene diisocyanate (1, 6-hexamethylene diisocyanate, HDI), 4, 4'-methylene-bis (phenylcarbimide) (4, 4'-methylenediphenyl diisocyanate, MDI) or 4, 4', 4 "-triphenylmethane triisocyanate (triphenylmethane-4, 4', 4 "-triisocyanate).Preferably, described polyisocyanates is MDI.
Preferably, hydrazine is shown in following formula III:
H
2NNH
2(Ⅲ)。
Should be understood that above-mentioned hindered phenol compound as shown in formula I, as described in polyisocyanates and hydrazine reaction should obtain a kind of mixture, the difunctional compound as shown in formula IV just as described in a kind of moiety in mixture.And the present invention can by controlling the mode of temperature of reaction, such as first add the wherein one of described hindered phenol compound or hydrazine at low temperatures, monolateral reaction is carried out with described polyisocyanates, question response to a certain extent after, the wherein another kind adding described hindered phenol compound or hydrazine again under room temperature continues to react, and in the mixture formed, major part is the difunctional compound as shown in formula IV.
Preferably, described difunctional compound be by the hindered phenol compound as shown in formula I at low temperatures with as described in after polyisocyanates reacts, then to obtain with hydrazine reaction.
Preferably, described hindered phenol compound, described polyisocyanates and hydrazine are to react with the molar ratio mixing close to 1:1:1.
In the present invention, the reaction of described hindered phenol compound, described polyisocyanates and hydrazine carries out in organic solvent.Preferably, described organic solvent can be selected from alkanes (such as: toluene, dimethylbenzene, benzene, normal hexane, normal heptane or hexanaphthene), ethers (such as: ether or butyl ether), acetonitrile, tetrahydrofuran (THF), acetone, butanone or DMF (DMF).In a particular embodiment of the present invention, described organic solvent is toluene.
It should be noted that in the synthesis step of described difunctional compound, the reaction sequence of above-mentioned raw materials hydrazine and described hindered phenol compound and described polyisocyanates can't have influence on obtained difunctional compound.Preferably, described hindered phenol compound is first reacted at low temperature with described polyisocyanates, adds hydrazine afterwards again and react, because hydrazine is liquid and boiling point is low, the advantage of this synthesis order is that surplus stock residual in product is less.
In the present invention, synthesize the range of reaction temperature of described difunctional compound between-5-200 DEG C, reaction initial temperature prior to (less than 25 DEG C) reaction under low temperature or normal temperature, is warming up to predetermined temperature of reaction when being reacted to a certain degree usually more gradually.Preferably, the range of reaction temperature synthesizing described difunctional compound is 0-100 DEG C.
Stablizer of the present invention can make an addition in organic materials, to reduce the physical characteristic change (such as xanthochromia) that organic materials produces because being subject to the environmental influences such as visible ray, UV-light, acid, alkali, high temperature or oxidation.
Described organic materials can be selected from following organic polymer base material:
1. polyolefins: such as polyethylene, polypropylene, polyisobutene, polyisoprene, polyhutadiene or its combination.
2. olefinic copolymer: such as ethylene/propene copolymer, propylene/1-butene, propylene/iso-butylene, propylene, divinyl, iso-butylene/isopentene, ethylene/alkyl acrylate, ethylene/alkyl methacrylic ester, ethylene/acrylic acid copolymer or its esters.
3. polystyrene type: such as polystyrene, poly-p-methylstyrene or poly alpha methylstyrene.
4. the multipolymer of vinylbenzene or alpha-methyl styrene and diene or acrylic acid derivative: the multipolymer of such as vinylbenzene and divinyl, the multipolymer of vinylbenzene and vinyl cyanide, phenylethylene/butadiene/alkyl acrylate copolymer, phenylethylene/butadiene/acrylonitrile copolymer, phenylethylene/maleic anhydride copolymer or styrene/acrylonitrile/alkylmethacrylate polymer.
5. the graft copolymer of vinylbenzene or alpha-methyl styrene: such as styrene-grafted polyhutadiene, styrene-grafted Butadiene and Acrylonitrile copolymer.
6. halogen containing polymers: the flat rubber of such as polychlorostyrene, polyvinyl chloride, poly-ethylene fluoride or the multipolymer (multipolymer of such as vinylchlorid and vinyl acetate) with Halogen monomer.
7. the homopolymer of cyclic ethers class or multipolymer: such as poly-alkyl glycol, polyethylene oxide or poly(propylene oxide).
8. polyoxymethylene (POM).
9. polyphenylene oxide (polyphenylene oxide) or polyphenylene sulfide (polyphenylene sulfide).
10. melamine polyurethanes (poly cyanuric urethane).
11. polymeric amide and amide copolymer: by the polymkeric substance of diamine compound and carboxylated compound condensation reaction, such as polyamide 6, polyamide 6/6,6/10,6/12 or 4/6, polymeric amide 12 etc.
12. poly-urea resin or urethane: by polymkeric substance or the oligopolymer of diamine compound or polyvalent alcohol and di-isocyanate reaction.
13. polycarbonate and polyester/carbonic ether.
14. unsaturated polyester resins: reacted by saturated or unsaturated dicarboxylic acid compound and polyol condensating and form, can add olefines as linking agent, also can add halide-containing and reduce flammable.
The U.S. resin of resistance to ware, urea resin, polycyanate ester or epoxy resin is contained in 15. thermosetting acrylic resins or acrylic resin.
The mixture of 16. above-mentioned polymkeric substance: such as PP/EPDM, PC/ABS, PC/PBT, POM/ thermoplasticity PU or PA/PPO.
Preferably, described organic polymer base material is urethane.
Preferably, with the gross weight of described organic polymer base material for 100wt%, the content range of described stablizer is 0.01 to 10wt%.More preferably, the content range of described stablizer is 0.01 to 2wt%, can reach oxidation resistant effect.
The difunctional compound of stablizer of the present invention can make an addition to separately in above-mentioned organic materials, also can form composition with other additive and make an addition in above-mentioned organic materials.Addition manner carries out extruding or ejection formation after can mixing with organic polymer base material before processing, also can add in organic materials manufacturing process or use in post-treatment.Such as stablizer of the present invention can being made an addition in polyvalent alcohol or isocyanic ester raw material together foams forms urethane.
Preferably, stablizer of the present invention also comprises at least one additive, to promote fast light, acid and alkali-resistance, the high temperature resistant or oxidation resistant characteristic for organic materials.
This additive can be selected from one or more materials following:
1. hindered phenol type antioxidant
1.1 alkylation list phenols: such as 2,6-bis--tert-butyl-4-methyl-Phenol, the 2-tertiary butyl-4,6-xylenol, 2,6-di-t-butyl-4-ethylphenols, 2,6-bis--tertiary butyl-4-normal-butyl phenol, 2,6-di-t-butyl-4-isobutyl-phenol, 2,6-bis--cyclopentyl-4-methylphenol, 2,6-bis--octadecyl-4-methylphenols, 2,4,6-thricyclohexyl phenol or 2,6-, bis--nonyl-4-methylphenol.
1.2 alkylation quinones: such as 2,6-bis--tertiary butyl-4-methoxyphenols or 2,5-, bis--Tert. Butyl Hydroquinone.
1.3 diphenyl sulfide phenols: such as 2,2'-sulfuration-bis--(6-tert-butyl-4-methyl-Phenol), 2,2'-sulfuration-bis--(4-octyl phenol), 4,4'-sulfuration-bis--(the 6-tertiary butyl-3-methylphenol) or 4,4'-sulfuration-bis--(the 6-tertiary butyl-2-methylphenol).
1.4 alkylidene bisphenols classes: such as 2,2'-methylene radical-bis-(6-tert-butyl-4-methyl-Phenol), 2,2'-methylene radical-bis-(the 6-tertiary butyl-4-ethylphenol), 2,2'-methylene radical-bis-[4-methyl-6-(Alpha-Methyl cyclohexyl)-phenol], 2,2'-methylene radical-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene radical-bis-(6-nonyl-4-methylphenol), 2,2'-methylene radical-bis-(4,6-, bis--tert.-butyl phenol), 2,2'-ethylidene-bis-(4,6-, bis--tert.-butyl phenol), 2,2'-ethylidene-bis--(the 6-tertiary butyl-4-isobutyl-phenol), 2,2'-methylene radical-bis-[6-(α-methylbenzyl)-4-nonyl phenol], 2,2'-methylene radical-bis-[6-(alpha, alpha-dimethylbenzyl)-4-nonyl phenol], 4,4'-methylene radical-bis--(2,6-, bis--tert.-butyl phenol), 4,4'-methylene radical-bis--(the 6-tertiary butyl-2-methylphenol), two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-butane of 1,1-, two (the 3-tertiary butyl-5-methyl-2-the hydroxy phenyl)-4-methylphenol of 2,6-, 1,1,3-tri--(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-butane, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-3-dodecyl-sulfo-butane of 1,1-or ethylene glycol-[3,3-pair-(the 3'-tertiary butyl-4'-hydroxy phenyl)-butyl ester].
1.5 benzyl compounds: such as 1,3,5 (3,5-, bis--tertiary butyl-4-hydroxy benzyl) sulphur or 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-Qiang Ji Benzyl yl) benzene.
1.6 amidation phenols: such as β-(3,5-, bis--alkyl-4 hydroxy phenyl) methyl acrylate and stearylamine react and amidated product.
1.7 β-(3,5-bis--alkyl-4-hydroxy phenyl) esters of acrylic acid: by β-(3,5-bis--alkyl-4-hydroxy phenyl) acrylate or methyl acrylate and monohydroxy-alcohol or polyhydric alcohol reacts or transesterification reaction and obtaining, this monohydroxy-alcohol or polyvalent alcohol can be selected from isooctyl alcohol, n-Octanol or C
7to C
9alcohol mixture, stearyl alcohol, 1,6-hexylene glycol, BDO, sulfuration ethyl glycol, diethyl ethylene glycol, triethyl ethylene glycol, tetramethylolmethane.Such as pentaerythritol four (3-(3,5-di-tert-butyl-hydroxy phenyl)) propionic ester (CAS No.229-722-6) or triethylene glycol two (3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl)) propionic ester (CAS No.36443-68-2).
1.8 β-(3,5-bis--alkyl-4-hydroxy phenyl) acrylic acid amides class: such as N, N-two-(3,5-bis--tert-butyl-hydroxy phenyl propenyl)-hexanediamine, N, N-two-(3,5-bis--tert-butyl-hydroxy phenyl propenyl)-propylene diamine, N, N-two-(3,5-bis--tert-butyl-hydroxy phenyl propenyl)-diamine, β-(3,5-, bis--tert-butyl-hydroxy phenyl) vinylformic acid-octadecyl amide or β-(3-methyl-5-tert-butyl-hydroxy phenyl) vinylformic acid-octadecyl amide.
2. UV light absorber and photostabilizer
2.12-(2'-hydroxy phenyl)-benzotriazole cpd: with substituents on such as phenyl, as 5'-methyl, 3', 5'-di-t-butyl, the 5'-tertiary butyl, 5'-(1,1,3,3-tetramethyl butyl), the chloro-3' of 5-, the chloro-3'-tertiary butyl of 5'-bis--tertiary butyl, 5--5'-methyl, the 3'-isobutyl--5'-tertiary butyl, 3', 5'-bis--tert-pentyl or 3', 5'-is two-benzotriazole cpd such as the benzotriazole cpd of (alpha, alpha-dimethylbenzyl) etc. or the derivative ester class of 2'-hydroxyl para postion tool vinylformic acid.
2.22-hydroxy benzophenone: with the benzophenone of 4-hydroxyl, 4-methoxyl group, 4-octyloxy, 4-certain herbaceous plants with big flowers oxygen base or 4-dodecyloxy.
The ester class that 2.3 phenylformic acid are derivative: such as 2,4-bis--tert-butyl-phenyls, 3,5-di-tert-butyl-4-hydroxybenzoic acid esters.
2.4 nickeliferous stablizers: the nickel coordination compound of such as 2,2'-sulfurations-bis-[4-(1,1,3,3-tetramethyl butyl)-phenol].
2.5 hindered amine type light stabilizer: such as two (2, 2, 6, 6-tetramethyl-piperidyl) sebate, 2-(3, 5-di-t-butyl-4-hydroxyl-benzene benzyl)-2-butyl 1, 3-propanedioic acid two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl)-sebate, 4, 4'-bis-(1, 2, 2, 6, 6-pentamethvl base) two phenylmethane [4, 4'-diphenylmethane bis (1, 2, 2, 6, 6-pentamethyl piperidyl carbamate)], 4, 4'-bis-(2, 2, 6, 6-tetramethyl-piperidyl) two phenylmethane [4, 4'-diphenylmethane bis (2, 2, 6, 6-tetramethyl piperidyl carbamate)], poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidine ethanol) ester [poly-(N-β-hydroxyethyl-2, 2, 6, 6-tetramethylpiperidine-4-hydroxy-piperidyl succinate) etc.
3. metal inactivator: such as N, N ,-bis-(3,5-di-t-butyl-4-coumarinyl acidic group) diamine.
4. the phosphorous organic oxidation-resistant agent such as phosphoric acid ester and phosphorous acid esters: such as triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two [2-methyl-4,6-bis-(1,1-dimethyl ethyl) phenol] ethyl ester (CAS No.14560-60-8), phosphorous acid dihydroxyphenyl propane ester, four (2,4-di-tert-butyl-phenyl-4,4'-xenyl) biphosphonate (CAS No.38613-77-3), tetramethylolmethane diphosphite two (stearyl alcohol) ester (CAS No.3806-34-8), two diphosphorous acid two (2, the 4-di-tert-butyl-phenyl) ester of tetramethylolmethane, two (2,6-di-t-butyl-4-tolyl) pentaerythritol phosphite, 2,4,6-tri-tert phenyl pentaerythritol bis-phosphite, tetramethylolmethane diphosphite two (decyl alcohol) ester, tetramethylolmethane diphosphite two (lauryl alcohol) ester, the condenses (mol ratio 1:2) of dipropylene glycol (DPG) and triphenyl phosphite or oligopolymer (as mol ratio 7:8) etc.
5. monothioester class antioxidant: such as Tyox B (CAS No.123-28-4), thio-2 acid two (13) ester (CAS No.10595-72-9), thio-2 acid two (14) ester (CAS No.16545-54-3) or thio-2 acid two (18) ester (CAS No.693-36-7).
6. Basic co-stabilisers: the organic stabilizers such as such as trimeric cyanamide, urea derivative, hydrazine derivatives, 1,1-dimethylhydrazine derivative, amine, hydroxyl-nitrogen key organic compound, alkalescence and alkaline earth metal salt, zeolite, hydrotalcite, calcium stearate, zinc, tin, magnesium.
7. nucleator: such as 4-p t butylbenzoic acid or hexanodioic acid.
8. filler or reinforcer: such as calcium carbonate, diatomite, glass fibre, asbestos (asbestos), talcum (talc), kaolin, mica, metal oxide or metal hydroxides, carbon black or graphite.
9. other additive: such as fluidizer, lubricant, emulsifying agent, interfacial agent, colorant, white dyes, fire retardant, static inhibitor or whipping agent.
Preferably, described additive is selected from hindered phenol type antioxidant, phosphorous organic oxidation-resistant agent, monothioester class antioxidant, hindered amine type light stabilizer or its combination.
Preferably, with the gross weight of described organic polymer base material for 100wt%, the content range of described additive is 0.01 to 10wt%.
The present invention will be described further with regard to following examples, but it should be understood that described embodiment is only explanation use of the present invention, and should not be used to limit scope of the invention process.
embodiment
Prepare difunctional compound
< comparative example 1 > compd A
250mL ethanol, 60g80% hydrazine hydrate and 146g β-(3 are added in 500mL tetra-neck mechanical stirring bottle, 5-bis--tert-butyl-hydroxy phenyl) methyl propionate, be warming up to backflow 6 hours, detect extremely without β-(3 with TLC, 5-bis--tert-butyl-hydroxy phenyl) methyl propionate, add 150mL water for cooling again, make product crystallization and separate out completely, after filtering drying, obtaining white solid powder 141g.
By another 500mL tetra-neck mechanical stirring bottle with after nitrogen deoxygenation, add 250mL toluene and 50g (0.2mol) 4, 4'-methylene-bis (phenylcarbimide) (MDI), 58.4g (0.2mol) above-mentioned white solid powder is slowly first added at 10-15 DEG C, exothermic phenomenon is had in adition process, temperature is made naturally to rise to 40-45 DEG C, react and add 12.6g (0.21mol) 1 again after 1 hour, 1-dimethylhydrazine (1, 1-dimethylhydrazine), have solid in process to produce, be warming up to 55-60 DEG C of reaction 3 hours, be warming up to 90 DEG C of reactions again after 2 hours, be cooled to 10 DEG C and filter out crystallization, obtain 109g white solid [namely as shown in the formula the compd A shown in (A)], its fusing point is 112-118 DEG C.
< embodiment 1 > difunctional compound B
The synthetic method of embodiment 1 is identical with comparative example 1, difference is in replacing 12.6g (0.21mol) 1 with 9.0g80% hydrazine hydrate, 1-dimethylhydrazine, obtain 104g white solid [namely as shown in the formula the difunctional compound B shown in (B)], its fusing point is 197-205 DEG C.
< embodiment 2 > difunctional compound C
The synthetic method of embodiment 2 is identical with comparative example 1, difference is in 33.6g1,6-hexamethylene diisocyanate (HDI) replaces 50g (0.2mol) MDI, and replace 12.6g (0.21mol) 1 with 9.0g80% hydrazine hydrate, 1-dimethylhydrazine, obtain 86.5g white solid [namely as shown in the formula the difunctional compound C shown in (C)], its fusing point is 128-135 DEG C.
< comparative example 2 > Compound D
The synthetic method of comparative example 2 is identical with comparative example 1, difference is in replacing 146g β-(3 with 125g β-(3-methyl-5-tert-butyl-hydroxy phenyl) methyl propionate, 5-bis--tert-butyl-hydroxy phenyl) methyl propionate, after reacting with hydrazine hydrate in ethanol, obtain intermediate product 101g.Get 50g (0.2mol) above-mentioned intermediate product and sequentially carry out reacting (step and consumption identical with comparative example 1) with MDI and 1,1-dimethylhydrazine, obtain 101g white solid [namely as shown in the formula the Compound D shown in (D)].
< comparative example 3 > mixture E
The synthetic method of comparative example 3 is identical with comparative example 2, difference is in by this intermediate product, MDI and 1, it is 1.34:1.0:0.67 that the relative usage of 1-dimethylhydrazine changes over mol ratio, the white solid obtained for the such as Compound D shown in above formula (D) with as shown in the formula the compd E shown in (E') ' mixture.
< embodiment 3 > difunctional compound F
250mL toluene, 61g thanomin and 146g β-(3 are added in 500mL tetra-neck mechanical stirring bottle, 5-bis--tert-butyl-hydroxy phenyl) methyl propionate, be warming up to backflow 18 hours, detect extremely without β-(3 with TLC, 5-bis--tert-butyl-hydroxy phenyl) methyl propionate, cooling makes its crystallization and separates out completely, and obtain white solid powder 143g after filtering drying, its fusing point is 136-138 DEG C.
By another 500mL tetra-neck mechanical stirring bottle with after nitrogen deoxygenation, add 250mL toluene and 50g (0.2mol) MDI, 64.2g (0.2mol) above-mentioned white solid powder is slowly first added at 20-25 DEG C, micro-exothermic phenomenon is had in adition process, react after 5 hours, temperature rises to 40-45 DEG C, continue reaction after 2 hours, add 12g (0.3mol) 80% hydrazine hydrate again, and react 3 hours at this temperature, have solid in process to produce, be warming up to 55-60 DEG C of stirring reaction 3 hours again, be cooled to 10 DEG C and filter out crystallization, obtain 110g white solid [namely as shown in the formula the difunctional compound F shown in (F)], its fusing point is 96-102 DEG C.
< embodiment 4 > difunctional compound G
0.67g Dibutyltin oxide (di-butyltin oxide), 136g (0.907mol) triglycol (triethylene glycol) and 105.5g (0.422mol) β-(3-methyl-5-tert-butyl-hydroxy phenyl) methyl propionate is added in 500mL tetra-neck mechanical stirring bottle, be warming up to 155-165 DEG C of reaction 7 hours, detect extremely without β-(3-methyl-5-tert-butyl-hydroxy phenyl) methyl propionate with TLC, steam excessive triglycol with molecular distillation, obtain the micro-yellow thick liquid of 125g.Analyze above-mentioned micro-yellow liquid with HPLC (movement is 80% methyl alcohol mutually), result is for 62wt% is as shown in the formula the monolateral product shown in (I-G) and the bilateral product of 38wt% { triethylene glycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl)] propionic ester }.
By another 500mL tetra-neck mechanical stirring bottle with after nitrogen deoxygenation, add 250mL toluene and 50g (0.2mol) MDI, the above-mentioned micro-yellow liquid of 118.7g (containing the monolateral product of 0.2mol) is slowly first added at 20-25 DEG C, micro-exothermic phenomenon is had in adition process, react after 5 hours, temperature rises to 40-45 DEG C, continue reaction after 2 hours, add 12g (0.3mol) 80% hydrazine hydrate again, and react 3 hours at this temperature, have solid in process to produce, be warming up to 55-60 DEG C of stirring reaction 3 hours again, colloidal solid [namely as shown in the formula the difunctional compound G shown in (G)] is obtained after heating volatilization toluene.
< comparative example 4 > compound H
The synthetic method of comparative example 4 is identical with comparative example 1, difference is in not adding 1,1-dimethylhydrazine, and the relative usage of this intermediate product and MDI is changed over mol ratio is 2.0:1.0, the white solid obtained is for as shown in the formula the compound H shown in (H).
Prepare the polymkeric substance through modification
By the difunctional compound of embodiment and comparative example 1, the compd A of 4, H respectively with thermoplastic polyurethane (TPU, purchased from TaiWan, China brothers company, model is 95A) mix (with TPU gross weight for 100wt%) according to the ratio of following table 1, and add additive according to the ratio of following table 1, obtain the TPU composition containing stablizer E1-E5 and CE1-CE3 respectively, after twin screw extruder (TaiWan, China Hong Yu Mechanology Inc. trier PSM20A) mixes extrusion at 195 DEG C, at 200 DEG C, the thick TPU polymkeric substance through modification of 2mm (ASTM-D638TYPE IV test piece) is penetrated into again through Jet forming machine (TaiWan, China hundred moulds company vertical ejaculator V2-S).
Table 1
Additive in Table 1 produced by TaiWan, China double bond chemical company, and wherein, Chinox245 represents " triethylene glycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl)] propionic ester ";
Chisorb1500 represents " two (N, N-dimethylhydrazine phosphinylidyne-4-aminophenyl) methane (Cas No.85095-61-0) ";
Chisorb770 represents " two (2,2,6,6-tetramethyl-piperidyl) sebate ";
Chisorb5411 represents " 2-(2'-hydroxy phenyl)-5'-(1,1,3,3-tetramethyl butyl) benzotriazole "; And
DLDTP represents " Tyox B ".
[color inhibition test]
< room temperature and the > of resistance to Thermal test
The above-mentioned polymkeric substance through modification is placed in respectively air at room temperature and 50 DEG C of baking ovens (purchased from German BINDER company, model is FD53L) in, and measure its colour-change and [utilize the color difference meter of HunterLab company (model is ColorQuest XE) to measure YI value, and calculate YI value ascending amount (Δ YI value)], result is as shown in table 2 below.
Table 2
Because Δ YI value is less, represent that its color inhibition effect is higher, therefore can be learnt by table 2, stablizer of the present invention has can resist oxynitride (NO
x) the hindered phenol compound (difunctional compound) of amine urea (semicarbazide) structure, so through the TPU of stablizer E1 (compd B) modification in room temperature and 50 DEG C of resistance to Thermal test, no matter after 30 days or 60 days, all present better color inhibition effect relative to the TPU composition through stablizer CE1, CE2 and CE3 modification.In addition, can be learnt by the test result of the TPU through stablizer E2-E5 modification, if the difunctional compound in stablizer of the present invention is with other additive and use, also multipotency presents the color inhibition effect better compared with the TPU through stablizer CE1, CE2 and CE3 modification after 60 days.
< alkaline-resisting test >
The above-mentioned polymkeric substance through modification is inserted in the ultrapure water of 500mL respectively, and add salt of wormwood adjusted to ph to 11, reheat to 80 DEG C, constant temperature is after 1 hour, the above-mentioned polymkeric substance through modification is taken out in air at room temperature, and measure its colour-change (Δ YI value), result is as shown in table 3 below.
Table 3
Can be learnt by table 3, through the TPU of stablizer E1-E5 of the present invention modification in alkaline-resisting test, no matter after 30 days, 45 days, 60 days or 70 days, better color inhibition effect is all presented relative to the TPU composition through stablizer CE1, CE2 and CE3 modification, show that stablizer of the present invention is owing to having the hindered phenol compound (difunctional compound) of amine urea structure, therefore has obvious alkaline-resisting advantage.
In sum, stablizer of the present invention is owing to having the hindered phenol compound (difunctional compound) of amine urea structure, therefore the color inhibition effect of organic polymer under room temperature, 50 DEG C and alkaline environment can significantly be promoted, and can with other additive and use, so really object of the present invention can be reached.
The above, be only preferred embodiment of the present invention, can not limit scope of the invention process with this, as long as the simple equivalence namely done according to the claims in the present invention and description changes and modifies, all still remains within the scope of the patent.
Claims (10)
1., for promoting a stablizer for organic materials weathering resistance, it is characterized in that it comprises the difunctional compound shown in following formula IV:
In formula IV,
R
1represent C
1to C
8alkyl;
R
2represent C
1to C
18alkylidene group, cycloalkylidene, arylidene, sub-aralkyl or alkarylene; And
X represent-NH-NH-or
Y
1and Y
2represent-O-or-NH-identical or differently; R represents C
1to C
6alkylidene group; And n represents 0 to 2.
2. stablizer according to claim 1, is characterized in that: R
2represent C
6to C
18alkylidene group or alkarylene.
3. stablizer according to claim 1, is characterized in that: X represents-NH-NH-and R
1represent the tertiary butyl.
4. stablizer according to any one of claim 1 to 3, is characterized in that: described difunctional compound is obtained by hindered phenol compound, polyisocyanates and the hydrazine reaction shown in following formula I:
5. stablizer according to claim 1, is characterized in that also comprising at least one additive.
6. stablizer according to claim 5, is characterized in that: described additive is selected from hindered phenol type antioxidant, phosphorous organic oxidation-resistant agent, monothioester class antioxidant, hindered amine type light stabilizer or its combination.
7. one kind polymer-modified, it is characterized in that it includes organic polymer base material, and the stablizer as described in claim 1 or 5.
8. according to claim 7 polymer-modified, it is characterized in that: described organic polymer base material is urethane.
9. according to claim 7 polymer-modified, it is characterized in that: with the gross weight of described organic polymer base material for 100wt%, the content range of described stablizer is 0.01 to 2wt%.
10. stablizer according to claim 7, is characterized in that: described stablizer is as claimed in claim 5, and with the gross weight of described organic polymer base material for 100wt%, the content range of described additive is 0.01 to 10wt%.
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| CN201310740562.5A CN104744726B (en) | 2013-12-27 | 2013-12-27 | For the polymer for lifting the stabilizer of organic material weatherability and being modified through it |
| KR1020140062872A KR101602560B1 (en) | 2013-12-27 | 2014-05-26 | Difunctional weather-resistant stabilizer and polymer composition containing the same |
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| KR102580674B1 (en) * | 2021-12-22 | 2023-09-19 | 한국화학연구원 | Method, apparatus and system of providing virutal weathering test service |
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|---|---|---|---|---|
| US3538046A (en) * | 1966-12-02 | 1970-11-03 | Bayer Ag | Polyurethanes stabilized with phenolic hydrazides |
| US3748357A (en) * | 1966-11-16 | 1973-07-24 | Bayer Ag | Semicarbazide with substituted phenyl group |
| US4164611A (en) * | 1975-07-10 | 1979-08-14 | Ciba-Geigy Corporation | Aromatic sulfonyl hydrazides and semicarbazides as chemical blowing agents |
| US5981065A (en) * | 1992-05-26 | 1999-11-09 | Union Carbide Chemicals & Plastics Technology Corporation | Telephone cables |
| CN1847478A (en) * | 2005-04-11 | 2006-10-18 | 日清纺绩株式会社 | polyurethane elastic fiber |
| CN102344389A (en) * | 2011-10-17 | 2012-02-08 | 姚建文 | Double-hindered phenol structure-contained hydrazides compound and preparation method thereof |
| CN102574973A (en) * | 2009-09-30 | 2012-07-11 | 拜尔材料科学股份公司 | Method for reducing emissions from polyurethane foams |
| CN102557991A (en) * | 2011-12-21 | 2012-07-11 | 蓬莱红卫化工有限公司 | Spandex anti-yellowing agent, and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI476193B (en) * | 2012-05-18 | 2015-03-11 | Fdc Lees Chemical Industry Co | A stabilizer with 1,1-dimethyl hydrazine functional group and its composition |
-
2013
- 2013-12-27 CN CN201310740562.5A patent/CN104744726B/en active Active
-
2014
- 2014-05-26 KR KR1020140062872A patent/KR101602560B1/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3748357A (en) * | 1966-11-16 | 1973-07-24 | Bayer Ag | Semicarbazide with substituted phenyl group |
| US3538046A (en) * | 1966-12-02 | 1970-11-03 | Bayer Ag | Polyurethanes stabilized with phenolic hydrazides |
| US4164611A (en) * | 1975-07-10 | 1979-08-14 | Ciba-Geigy Corporation | Aromatic sulfonyl hydrazides and semicarbazides as chemical blowing agents |
| US5981065A (en) * | 1992-05-26 | 1999-11-09 | Union Carbide Chemicals & Plastics Technology Corporation | Telephone cables |
| CN1847478A (en) * | 2005-04-11 | 2006-10-18 | 日清纺绩株式会社 | polyurethane elastic fiber |
| CN102574973A (en) * | 2009-09-30 | 2012-07-11 | 拜尔材料科学股份公司 | Method for reducing emissions from polyurethane foams |
| CN102344389A (en) * | 2011-10-17 | 2012-02-08 | 姚建文 | Double-hindered phenol structure-contained hydrazides compound and preparation method thereof |
| CN102557991A (en) * | 2011-12-21 | 2012-07-11 | 蓬莱红卫化工有限公司 | Spandex anti-yellowing agent, and preparation method and application thereof |
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|---|---|
| KR101602560B1 (en) | 2016-03-10 |
| KR20150077260A (en) | 2015-07-07 |
| CN104744726B (en) | 2017-09-05 |
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Effective date of registration: 20180411 Address after: No. 8, Shu Gang Road, Taixing Economic Development Zone, Taixing, Jiangsu Patentee after: Double key chemical (Taixing) Co., Ltd. Address before: No. 135, No. 135, Roosevelt Road, Taiwan, Taiwan, China Co-patentee before: New Network Limited Patentee before: FDC Lees Chemical Industry Co., Ltd. |