CN1660823A - 低厚度的透明聚合物制品 - Google Patents
低厚度的透明聚合物制品 Download PDFInfo
- Publication number
- CN1660823A CN1660823A CN2005100518986A CN200510051898A CN1660823A CN 1660823 A CN1660823 A CN 1660823A CN 2005100518986 A CN2005100518986 A CN 2005100518986A CN 200510051898 A CN200510051898 A CN 200510051898A CN 1660823 A CN1660823 A CN 1660823A
- Authority
- CN
- China
- Prior art keywords
- butyl
- phenyl
- acid
- ester
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 150000001875 compounds Chemical class 0.000 claims description 60
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- -1 polyethylene Polymers 0.000 abstract description 155
- 239000004743 Polypropylene Substances 0.000 abstract description 24
- 150000001412 amines Chemical class 0.000 abstract description 20
- 229920000098 polyolefin Polymers 0.000 abstract description 20
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical compound OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 abstract description 16
- 229920001155 polypropylene Polymers 0.000 abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004698 Polyethylene Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 230000005855 radiation Effects 0.000 abstract description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000813 microbial effect Effects 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 63
- 150000002148 esters Chemical class 0.000 description 41
- 239000000203 mixture Substances 0.000 description 40
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 39
- 238000010521 absorption reaction Methods 0.000 description 31
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- 239000000654 additive Substances 0.000 description 18
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- 239000002585 base Substances 0.000 description 16
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 150000001408 amides Chemical class 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 11
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229940059574 pentaerithrityl Drugs 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 6
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000002688 persistence Effects 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- PMNGNPRHPYYVNM-UHFFFAOYSA-N 1-hydroxyundecane-3-sulfonic acid Chemical compound CCCCCCCCC(CCO)S(O)(=O)=O PMNGNPRHPYYVNM-UHFFFAOYSA-N 0.000 description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
- ICHKVCYUNCKCGL-UHFFFAOYSA-N CN(C)C.OCCCCCCO Chemical compound CN(C)C.OCCCCCCO ICHKVCYUNCKCGL-UHFFFAOYSA-N 0.000 description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000002429 hydrazines Chemical class 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- COVMBDWAODLWIB-UHFFFAOYSA-N n'-(2-hydroxyethyl)oxamide Chemical compound NC(=O)C(=O)NCCO COVMBDWAODLWIB-UHFFFAOYSA-N 0.000 description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
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- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 3
- 150000000182 1,3,5-triazines Chemical class 0.000 description 3
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 3
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Abstract
这里公开了新型的透明聚烯烃、聚酯或聚酰胺制品,它通过添加0.005-0.30重量%(基于聚合物基材)的羟苯基三嗪UV吸收剂得到稳定化而能够抵抗光、氧、热和侵蚀性化学品的影响,并且以其在1和500微米之间的厚度为特征。如此被稳定的优选聚烯烃制品是含有位阻胺作为附加稳定剂的农膜。该新型的组合物用作选择性UV过滤剂,尤其用于农业中。
Description
本申请是中国专利申请01123084.3的分案申请。
技术领域
本发明涉及具有在抵抗光、氧、热和侵蚀性化学品的作用方面有提高的稳定性的低厚度和良好透明度的新型聚合物制品,它也可有效地作为农业应用上的选择性UV过滤材,并且涉及适合于这一应用的一些新型稳定剂。
背景技术
含有羟苯基三嗪类型的UV吸收剂的某些聚烯烃制品可从GB-A-2319523,EP-A-704437,EP-A-704560,WO 99/57189中获知。
发明内容
本发明涉及通过添加相当于聚合物基材的0.005-0.30重量%的羟苯基三嗪UV吸收剂来加以稳定的透明聚烯烃、聚酯或聚酰胺制品,特征在于该制品具有在1-500μm(微米)之间的厚度。
优选的制品含有通式I的化合物作为羟苯基三嗪UV吸收剂
其中
R1是H或OR7;
R2和R3独立地是H,C1-C8烷基,
R4和R5独立地是H,C1-C8烷基,OR10;
R6是H,C1-C18烷基,C5-C12环烷基,C7-C12苯基烷基,C7-C12烷基苯基,C3-C12链烯基,卤素,OH,OR9;
R8是H;卤素;C1-C12烷氧基;C1-C12烷基;被氧插入和/或被OH取代的C3-C24烷基;或是NH-CO-R14或NH-COO-R12;
R7,R9和R10独立地是H;C1-C24烷基;C3-C12链烯基;被氧插入和/或被OH取代的C3-C24烷基;或是C5-C12环烷基,C7-C12苯基烷基,C7-C12烷基苯基;CH2CH(OH)CH2OR11;被COOR12、CONR13R14、OCOR15、OH或卤素取代的C1-C12烷基;或R7是具有10-1000个碳原子,优选20-500个碳原子的聚合烃残基;
和R7还包含通式II的残基
其中X是C2-C24亚烷基;-CH2CH(OH)CH2-;-CH2CH(OH)CH2O-D-OCH2CH(OH)CH2;(C1-C18亚烷基)-CO-O-D-O-CO-(C1-C18亚烷基);CO;CO-(C2-C24亚烷基)-CO;被氧插入的C3-C24亚烷基;
D是C2-C12亚烷基;被O插入的C4-C50亚烷基;亚苯基;亚联苯基或亚苯基-E-亚苯基;
E是O,S,SO2;CH2;CO或-C(CH3)2-;
R11是H,C1-C12烷基;苯基;被1-3个C1-C4烷基取代的苯基;C5-C12环烷基;C7-C12苯基烷基;C3-C12链烯基;
R12是H;C1-C24烷基;C3-C12链烯基;被氧插入和/或被OH取代的C3-C36烷基;或是C5-C12环烷基,C7-C12苯基烷基,C7-C12烷基苯基;苯基;
R13和R14独立地是H,C1-C18烷基;苯基;被1-3个C1-C4烷基和/或C1-C4烷氧基取代的苯基;C5-C12环烷基;C3-C12链烯基;
R15是C1-C12烷基;苯基;被1-3个C1-C4烷基和/或C1-C4烷氧基取代的苯基;C5-C12环烷基;C3-C12链烯基;C1-C12烷氧基;或是NR13R14。
更优选地,在通式I的羟苯基三嗪UV吸收剂中
R4和R5独立地是H或甲基;
R6是H;
R8是H;C1-C8烷氧基;C1-C8烷基;
R7,R9独立地是H;C1-C18烷基;C3-C12链烯基;被氧插入和/或被OH取代的C3-C24烷基;或是C5-C12环烷基,C7-C12苯基烷基,C7-C12烷基苯基;被COOR12、OCOR15、OH取代的C1-C12烷基;或R7是具有20-500个碳原子的聚合烃残基;
和R7也可包括通式II的残基,其中X是C2-C18亚烷基;-CH2CH(OH)CH2-;-CH2CH(OH)CH2O-D-OCH2CH(OH)CH2;(C1-C4亚烷基)-CO-O-D-O-CO-(C1-C4亚烷基);CO;CO-(C2-C18亚烷基)-CO;被氧插入的C3-C18亚烷基;D是C2-C12亚烷基;
R12是H;C1-C24烷基;C3-C12链烯基;被氧插入和/或被OH取代的C3-C24烷基;或是C5-C12环烷基,C7-C12苯基烷基,C7-C12烷基苯基;苯基;
R15是C1-C12烷基;C5-C12环烷基;C3-C12链烯基;
尤其
R1是OR7;
R2和R3独立地是H,甲基,
OR9;
R4和R5和R6是H;
R8是H;C1-C8烷氧基;C1-C4烷基;
R7,R9独立地是C4-C18烷基或C5-C12环烷基;
R7也包括通式II的残基,其中X是C4-C18亚烷基。
极重要的是通式I的化合物,其中R1是OR7;R2和R3各是苯基;R4,R5和R6是氢;和R7是C4-C18烷基或C5-C12环烷基或通式II的残基,其中X是C4-C12亚烷基。
卤素取代基是-F,-Cl,-Br或-I,优选-F,-Cl或-Br,尤其优选,-Cl。
烷基苯基是烷基取代的苯基;C7-C14烷基苯基包括诸如甲基苯基(甲苯基),二甲基苯基(二甲苯基),三甲基苯基(_基),乙基苯基,丙基苯基,丁基苯基,二丁基苯基,戊基苯基,己基苯基,庚基苯基和辛基苯基。
苯基烷基是苯基取代的烷基;C7-C11苯基烷基包括诸如苄基,α-甲基苄基,α-乙基苄基,α,α-二甲苄基,苯基乙基,苯丙基,苯基丁基和苯基戊基。
n-烷基或烷基-n是未支化的烷基。
被O、NH,NR13等插入的烷基一般能够包括一个或多个不相邻的杂原子。优选烷基链的碳原子键接于不多于1个杂原子上。作为被COOR12取代的烷基,R7,R9和R10,尤其R7,最优选是CH2-COOR12。R12最优选是C1-C18烷基,或C6-C12环烷基;环烷基最优选是环己基或环十二烷基。
在所述定义的范围内,作为烷基的基团R4,R5,R6,R8,R9,R11,R12,R13,R14,R15是支化或非支化的烷基,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,十三烷基,十四烷基,十五烷基,十六烷基,十七烷基和十八烷基。
C1-C4烷基尤其是甲基,乙基,异丙基,正丁基,2-丁基,2-甲基丙基或叔丁基。
在所述定义范围内,作为链烯基的R4,R5,R6,R8,R9,R11,R12,R13,R14,R15包括烯丙基,异丙烯基,2-丁烯基,3-丁烯基,异丁烯基,正戊-2,4-二烯基,3-甲基-丁-2-烯基。
R4,R5和R6最优选是氢。R2和R3最优选是苯基或OR9,尤其苯基。R9最优选是C1-C4烷基。
通式I的高度有效的化合物的例子是以下所列的或在下表中:
2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2,4-二羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十三烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-丁氧基-丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-辛氧基-丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基-苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-十二烷氧基-丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪,2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪,2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基-丙氧基)苯基]-1,3,5-三嗪,2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪,2-{2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪。
表1:下式的化合物
化合物 R7
a) CH2CH(C2H5)-(CH2)3-CH3
b) CH(CH3)-(CH2)9-CH3
c) n-C6H13
d) n-C8H17
e) n-C12H25
在以上定义中,n表示直链烷基链。
表2:下式(k)的化合物
化合物 X
f) -(CH2)12-
g) -(CH2)10-
或其中X是以下基团的对应化合物:C13-C24亚烷基;(C1-C18亚烷基)-CO-O-D-O-CO-(C1-C18亚烷基);CO-(C13-C24亚烷基)-CO;插入氧的C3-C24亚烷基,尤其(C1-C3亚烷基)-O-(C1-C3亚烷基)。
通式I的高度有效的化合物的其它例子是以下化合物:
通式I的一些化合物是已知的,例如从WO 96/28431,US-5591850,EP-A 434608获知;其它化合物,例如以下化合物
以及(b),(f),(g)和(h)是新型化合物。它们可以方便地按照与这些文献中所述过程类似、尤其与WO 96/28431的实施例18中给出的方法类似的方法制备。
聚合物膜(尤其本发明的聚烯烃薄膜)的特别有用的应用是它们用作棚膜。一些类型的作物受到太阳辐射的UV-组分的损害,必须将它滤掉以获得高质量和生产率的作物。另外,一些微生物如真菌,例如灰葡萄孢,Botryosporium,芽枝霉属cucumerium,地内孢霉,扣囊拟内孢霉,蔷薇单丝壳,亚麻白粉菌,Gonatobotrys,柱盘孢菌,镰孢霉属,根念珠属,轮枝孢菌属,和病毒,例如Cucumo-病毒,Tombus-病毒等以及一些有害昆虫,例如粉虱,蚜虫,牧草虫或潜叶蝇,会在优选的特定UV照射下增殖。当UV光没有或较少到达植物时,这些害虫能够显著减少。IR.Reuveni等人,用于控制温室生长作物的叶病原体的光选择性PE膜的发展,Plasticulture No.102,p.7(1994);Y.Antignus等人,UV吸收塑料膜保护作物抵抗昆虫和病毒性疾病的传播的用途,CIPA Congress March 1997,pp.23-33]。另一方面,需求一定谱宽的紫外线辐射的蜜蜂活性应该在温室中得到保持,为的是确保在有花植物例如番茄,黄瓜,南瓜,西瓜,柠檬,玫瑰,草莓,莴苣,葡萄,胡椒等上结果实。
本发明的羟苯基三嗪UV吸收剂在聚烯烃,聚酯或聚酰胺中显示出优良的相容性和持久性。同时,这些UV吸收剂提供高效和选择性的UV屏蔽,以便在受保护的环境(尤其作物栽培)中抑制微生物繁衍,而与此同时保留了为蜜蜂、大黄蜂活性所必需的UV辐射。因此,本发明还涉及如上所述的透明聚烯烃薄膜在受保护的栽培中抑制微生物繁衍的用途。
用于制造本发明的制品的聚烯烃例子包括下列聚合物:
1.单烯烃和二烯烃的聚合物,例如聚丙烯,聚异丁烯,聚丁烯-1,聚-4-甲基戊烯-1,聚异戊二烯或聚丁二烯,以及环状烯烃如环戊烯或降冰片烯的聚合物,聚乙烯(任选地加以交联),例如高密度聚乙烯(HDPE),高密度和高分子量聚乙烯(HDPE-HMW),高密度和超高分子量聚乙烯(HDPE-UHMW),中等密度聚乙烯(MDPE),低密度聚乙烯(LDPE),线性低密度聚乙烯(LLDPE),(VLDPE)和(ULDPE)。
聚烯烃,即在前面的段落中例举的单烯烃的聚合物,优选聚乙烯和聚丙烯,能够通过不同的方法,和优选通过下面的方法来制备:
a)自由基聚合反应(一般在高压和升高的温度下)。
b)使用一般含有一种或一种以上元素周期表中IVb,Vb,VIb或VIII族金属的催化剂的催化聚合反应。这些金属通常具有一个或一个以上的配位体,典型的是π键或σ键配位的氧化物,卤化物,醇化物,酯类,醚类,胺类,烷基类,链烯基类和/或芳基类。这些金属配合物可以是游离形式或被固定在基底上,典型地在活化氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可以溶于或不溶于聚合反应介质。该催化剂本身可用于聚合反应或另外使用活化剂,典型的是金属烷基化物,金属氢化物,金属烷基卤化物,金属烷基氧化物或金属烷基噁烷(alkyloxanes),该金属是元素周期表的Ia,IIa和/或IIIa族的元素。活化剂可以方便地另外用酯,醚,胺或甲硅烷基醚基团改性。这些催化剂体系通常被命名为Phillips,Standard Oil Indiana,Ziegler(-Natta),TNZ(Dupont),金属茂或单中心催化剂(SSC)。
2.在以上1)项提到的聚合物的混合物,例如聚丙烯与聚异丁烯的混合物,聚丙烯与聚乙烯的混合物(例如PP/HDPE,PP/LDPE)和不同类型的聚乙烯的混合物(例如LDPE/HDPE)。
3.聚烯烃共聚物:单烯烃和二烯烃的共聚物,或单烯烃和二烯烃与其它乙烯基单体的共聚物,例如乙烯/丙烯共聚物,线性低密度聚乙烯(LLDPE)和它与低密度聚乙烯(LDPE)的混合物,丙烯/丁烯-1共聚物,丙烯/异丁烯共聚物,乙烯/丁烯-1共聚物,乙烯/己烯共聚物,乙烯/甲基戊烯共聚物,乙烯/庚烯共聚物,乙烯/辛烯共聚物,丙烯/丁二烯共聚物,异丁烯/异戊二烯共聚物,乙烯/丙烯酸烷基酯共聚物,乙烯/甲基丙烯酸烷基酯共聚物,乙烯/乙酸乙烯酯共聚物和它们与一氧化碳的共聚物或乙烯/丙烯酸共聚物和它们的盐类(离子交联聚合物)以及乙烯与丙烯和二烯烃如己二烯、二环戊二烯或1,1-亚乙基-降冰片烯的三元共聚物;和此类共聚物相互之间的混合物和与以上1)项中提到的聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物,LDPE/乙烯-乙酸乙烯酯共聚物(EVA),LDPE/乙烯-丙烯酸共聚物(EAA),LLDPE/EVA,LLDPE/EAA和交替或无规聚亚烷基/一氧化碳共聚物和它们与其它聚合物如聚酰胺的混合物。
用于制造本发明制品的聚酯主要是从二羧酸和二醇和/或从羟基羧酸或相应内酯形成的那些,例如聚对苯二甲酸乙二醇酯,聚对苯二甲酸丁二醇酯,聚对苯二甲酸1,4-二羟甲基环己烷酯,聚萘二甲酸亚烷基酯(PAN)和聚羟基苯甲酸酯,以及从羟基终端的聚醚形成的嵌段共聚醚酯;还有用聚碳酸酯或MBS改性的聚酯。优选的是聚对苯二甲酸乙二醇酯(PET)。
聚酰胺通常是从二胺和二羧酸和/或从氨基羧酸或相应的内酰胺形成的那些,例如聚酰胺4,聚酰胺6,聚酰胺6/6,6/10,6/9,6/12,4/6,12/12,聚酰胺11,聚酰胺12,从间二甲苯二胺和己二酸形成的芳族聚酰胺;从六亚甲基二胺和间苯二甲酸或/和对苯二甲酸制备的且有或没有弹性体作为改性剂的聚酰胺,例如聚对苯二甲酰2,4,4-三甲基六亚甲基二胺或聚间苯二甲酰间亚苯基二胺;上述聚酰胺与聚烯烃,烯烃共聚物,离子交联聚合物或化学键接或接枝弹性体的嵌段共聚物;或与聚醚,例如与聚乙二醇,聚丙二醇或聚丁二醇的嵌段共聚物;以及用EPDM或ABS改性的聚酰胺或共聚酰胺;和在加工过程中缩合的聚酰胺(RIM聚酰胺体系)。
最优选的是聚烯烃如聚乙烯,尤其优选低密度聚乙烯或线性低密度聚乙烯,或聚丙烯。
优选地,羟苯基三嗪UV吸收剂在本发明的透明聚合物制品中的量是该聚合物基材的0.005-0.15%,更优选0.005-0.06%,尤其优选0.01-0.06重量%。
本发明的透明聚烯烃、聚酯或聚酰胺制品通常是膜,纤维,丝带或拉伸带材,尤其是农膜。它的厚度优选是在1和300微米之间,尤其在1和200微米之间。本发明的膜,丝带或带材通常没有双轴取向。本发明的透明聚烯烃、聚酯或聚酰胺制品常常含有一种或多种其它组分,该组分例如选自其它的光稳定剂,加工稳定剂,填料,澄清剂,改性剂,除酸剂,颜料,阻燃剂或现有技术中已知的其它添加剂。 这些组分通常不会有效阻断光透过本发明的制品,透光率通常是超过白色入射光的20%,常常高于50%,和优选超过80%。为了足够的透明度,本发明的制品优选不含有其量显著损害这一性能的结晶组分;它们优选不含有颜料和不含有或含有仅仅少量(例如聚合物的0-5重量%)的比颜料(例如水滑石)有更低不透明化效果的填料或结晶无机组分。可在本发明的聚合物制品中含有的附加组分的例子包括下列这些:
1.抗氧化剂
1.1
烷基化一元酚类,例如,2,6-二叔丁基-4-甲基苯酚,2-叔丁基-4,6-二甲基苯酚,2,6-二叔丁基-4-乙基苯酚,2,6-二叔丁基-4-正丁基苯酚,2,6-二叔丁基-4-异丁基苯酚,2,6-二环戊基-4-甲基苯酚,2-(α-甲基环己基)-4,6-二甲基苯酚,2,6-双十八烷基-4-甲基苯酚,2,4,6-三环己基苯酚,2,6-二叔丁基-4-甲氧基甲基苯酚;壬基苯酚类,它是线性的或在支链上支化,例如2,6-二壬基-4-甲基苯酚,2,4-二甲基-6-(1′-甲基十一烷-1′-基)苯酚,2,4-二甲基-6-(1′-甲基十七烷-1′-基)苯酚,2,4-二甲基-6-(1′-甲基十三烷-1′-基)苯酚;以及它们的混合物。
1.2烷基硫代甲基酚类,例如2,4-二辛基硫代甲基-6-叔丁基苯酚,2,4-二辛基硫代甲基-6-甲基苯酚,2,4-二辛基硫代甲基-6-乙基苯酚,2,6-双十二烷基硫代甲基-4-壬基苯酚。
1.3氢醌类或烷基化氢醌类,例如,2,6-二叔丁基-4-甲氧基苯酚,2,5-二叔丁基氢醌,2,5-二叔戊基氢醌,2,6-二苯基-4-十八烷氧基苯酚,2,6-二叔丁基氢醌,2,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯甲醚,硬脂酸3,5-二叔丁基-4-羟基苯基酯,己二酸双(3,5-二叔丁基-4-羟基苯基)酯。
1.4生育酚,例如α-生育酚,β-生育酚,γ-生育酚,δ-生育酚和它们的混合物(维生素E)。
1.5羟基化硫代二苯基醚类,例如,2,2′-硫代双(6-叔丁基-4-甲基苯酚),2,2′-硫代双(4-辛基苯酚),4,4′-硫代双(6-叔丁基-3-甲基苯酚),4,4′-硫代双(6-叔丁基-2-甲基苯酚),4,4′-硫代双(3,6-二仲戊基苯酚),4,4’-双(2,6-二甲基-4-羟基苯基)二硫化物。
1.6亚烷基双酚类,例如,2,2′-亚甲基双(6-叔丁基-4-甲基苯酚),2,2′-亚甲基双(6-叔丁基-4-乙基苯酚),2,2′-亚甲基双[4-甲基-6-(α-甲基环己基)苯酚],2,2′-亚甲基双(4-甲基-6-环己基苯酚),2,2′-亚甲基双(6-壬基-4-甲基苯酚),2,2′-亚甲基双(4,6-二叔丁基苯酚),2,2′-亚乙基双(4,6-二叔丁基苯酚),2,2′-亚乙基双(6-叔丁基-4-异丁基苯酚),2,2′-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚],2,2′-亚甲基双[6-(α,α-二甲基苄基)-4-壬基苯酚],4,4′-亚甲基双(2,6-二叔丁基苯酚),4,4′-亚甲基双(6-叔丁基-2-甲基苯酚),1,1′-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷,2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚,1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷,1,1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷,双[3,3-双(3′-叔丁基-4′-羟基苯基)丁酸]乙二醇酯,双(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯,对苯二甲酸双[2-(3′-叔丁基-2′-羟基-5′-甲基苄基)-6-叔丁基-4-甲基苯基]酯,1,1-双-(3,5-二甲基-2-羟基苯基)丁烷,2,2-双-(3,5-二叔丁基-4-羟基苯基)丙烷,2,2-双-(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷,1,1,5,5-四-(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7.O-,N-和S-苄基化合物类,例如3,5,3′,5′-四叔丁基-4,4′-二羟基二苄基醚,4-羟基-3,5-二甲基苄基巯基乙酸十八烷基酯,4-羟基-3,5-二叔丁基苄基巯基乙酸十三烷基酯,三(3,5-二叔丁基-4-羟基苄基)胺,二硫代对苯二甲酸双(4-叔丁基-3-羟基-2,6-二甲基苄基)酯,双(3,5-二叔丁基-4-羟基-苄基)硫醚,3,5-叔丁基-4-羟基苄基巯基乙酸异辛基酯。
1.8羟苄基化丙二酸酯类,例如,2,2-双-(3,5-二叔丁基-2-羟基苄基)丙二酸二(十八烷基)酯,2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸二(十八烷基)酯,2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸二(十二烷基巯基乙基)酯,2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸双[4-(1,1,3,3-四甲基丁基)苯基]酯。
1.9芳族羟苄基化合物类,例如1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯,1,4-双(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯,2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯酚。
1.10三嗪化合物类,例如2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪,2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯,2,4,6-三(3,5-二叔丁基-4-羟基苯基乙基)-1,3,5-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰基)-六氢-1,3,5-三嗪,1,3,5-三(3,5-二环己基-4-羟基苄基)异氰脲酸酯。
1.11苄基膦酸酯类,例如2,5-二叔丁基-4-羟基苄基膦酸二甲酯,3,5-二叔丁基-4-羟基苄基膦酸二乙酯,3,5-二叔丁基-4-羟基苄基膦酸二(十八烷基)酯,5-叔丁基-4-羟基-3-甲基苄基膦酸二(十八烷基)酯,3,5-二叔丁基-4-羟基苄基膦酸的单乙酯的钙盐。
1.12酰基氨基酚类,例如4-羟基月桂酰苯胺,4-羟基硬脂酰苯胺,N-(3,5-二叔丁基-4-羟基苯基)氨基甲酸辛酯。
1.13β-(3,5-二叔丁基-4-羟基苯基)丙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯类。
1.14β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷,3,9-双[2-{3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基)-1,1-二甲基乙基]-2,4,8,10-四氧杂螺旋[5.5]-十一烷的酯类。
1.15β-(3,5-二环己基-4-羟基苯基)丙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯类。
1.16 3,5-二叔丁基-4-羟基苯基乙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯类。
1.17β-(3,5-二叔丁基-4-羟基苯基)丙酸的酰胺类,例如N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)三亚甲基二胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼,N,N’-双[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰氧基)乙基]草酰胺(Naugard_XL-1,由Uniroyal提供)。
1.18抗坏血酸(维生素C)
1.19胺类抗氧化剂,例如N,N′-二异丙基-对-亚苯基二胺,N,N′-二仲丁基-对-亚苯基二胺,N,N′-双(1,4-二甲基戊基)-对-亚苯基二胺,N,N′-双(1-乙基-3-甲基戊基)-对-亚苯基二胺,N,N’-双(1-甲基庚基)-对亚苯基二胺,N,N’-二环己基-对亚苯基二胺,N,N′-二苯基-对-亚苯基二胺,N,N′-双(2-萘基)-对-亚苯基二胺,N-异丙基-N′-苯基-对-亚苯基二胺,N-(1,3-二甲基丁基)-N′-苯基-对-亚苯基二胺,N-(1-甲基庚基)-N′-苯基-对-亚苯基二胺,N-环己基-N′-苯基-对-亚苯基二胺,4-(对甲苯氨磺酰基)二苯胺,N,N′-二甲基-N,N′-二仲丁基-对亚苯基二胺,二苯胺,N-烯丙基二苯胺,4-异丙氧基-二苯胺,N-苯基-1-萘基胺,N-(4-叔辛基苯基)-1-萘基胺,N-苯基-2-萘基胺,辛基化二苯胺(例如p,p′-二叔辛基二苯胺),4-正丁基氨基苯酚,4-丁酰氨基苯酚,4-壬酰氨基苯酚,4-十二酰氨基苯酚,4-十八酰氨基苯酚,双(4-甲氧基苯基)胺,2,6-二叔丁基-4-二甲氨基甲基苯酚,2,4′-二氨基二苯基甲烷,4,4′-二氨基二苯基甲烷,N,N,N′,N′-四甲基-4,4′-二氨基二苯基甲烷,1,2-双[(2-甲基苯基)氨基]乙烷,1,2-双(苯基氨基)丙烷,(邻甲苯基)双胍,双[4-(1′,3′-二甲基丁基)苯基]胺,叔辛基化N-苯基-1-萘基胺,单和二烷基化叔丁基/叔辛基二苯基胺类的混合物,单和二烷基化壬基二苯基胺类的混合物,单和二烷基化十二烷基二苯基胺类的混合物,单和二烷基化异丙基/异己基二苯基胺类的混合物,单和二烷基化叔丁基二苯基胺类的混合物,2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪,吩噻嗪,单和二烷基化叔丁基/叔辛基吩噻嗪的混合物,单和二烷基化叔辛基吩噻嗪的混合物,N-烯丙基吩噻嗪,N,N,N′,N′-四苯基-1,4-二氨基丁-2-烯,N,N-双(2,2,6,6-四甲基-哌啶-4-基-六亚甲基二胺,双(2,2,6,6-四甲基-哌啶-4-基)癸二酸酯,2,2,6,6-四甲基哌啶-4-酮,2,2,6,6-四甲基哌啶-4-醇。
2.UV吸收剂和光稳定剂
2.1
2-(2′-羟基苯基)苯并三唑类,例如2-(2′-羟基-5′-甲基苯基)苯并三唑,2-(3′,5′-二叔丁基-2′-羟基苯基)苯并三唑,2-(5′-叔丁基-2′-羟基苯基)苯并三唑,2-(2′-羟基)-5′-(1,1,3,3-四甲基丁基)苯基)苯并三唑,2-(3′,5′-二叔丁基-2′-羟基苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-甲基苯基)-5-氯-苯并三唑,2-(3′-仲丁基-5′-叔丁基-2′-羟基苯基)苯并三唑,2-(2′-羟基-4′-辛氧基苯基)苯并三唑,2-(3′,5′-二叔戊基-2′-羟基苯基)苯并三唑,2-(3′,5′-双-(α,α-二甲基苄基)-2′-羟基苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)-羰基乙基]-2′-羟基苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)羰基乙基]-2′-羟基苯基)苯并三唑,2-(3′-十二烷基-2′-羟基-5′-甲基苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-异辛氧基羰基乙基)苯基苯并三唑,2,2′-亚甲基-双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];2-[3′-叔丁基-5′-(2-甲氧基羰基乙基)-2′-羟基苯基]-2H-苯并三唑与聚乙二醇300的酯基转移产物;[R-CH2CH2-COO-CH2CH2-]2-其中R=3′-叔丁基-4′-羟基-5′-2H-苯并三唑-2-基苯基,2-[2’-羟基-3’-(α,α-二甲基苄基)-5’-(1,1,3,3-四甲基丁基)苯基]苯并三唑;2-[2’-羟基-3’-(1,1,3,3-四甲基丁基)-5’-(α,α-二甲基苄基)苯基]苯并三唑。
2.2 2-羟基二苯甲酮类,例如4-羟基,4-甲氧基,4-辛氧基,4-癸氧基,4-十二烷氧基,4-苄氧基,4,2′,4′-三羟基和2′-羟基-4,4′-二甲氧基衍生物。
2.3取代的和未取代的苯甲酸的酯类,例如水杨酸4-叔丁基-苯基酯,水杨酸苯酯,水杨酸辛基苯酯,二苯甲酰基间苯二酚,双(4-叔丁基苯甲酰基)间苯二酚,苯甲酰基间苯二酚,3,5-二叔丁基-4-羟基苯甲酸2,4-二叔丁基苯基酯,3,5-二叔丁基-4-羟基苯甲酸十六烷基酯,3,5-二叔丁基-4-羟基苯甲酸十八烷基酯,3,5-二叔丁基-4-羟基苯甲酸2-甲基-4,6-二叔丁基苯基酯。
2.4丙烯酸酯类,例如α-氰基-β,β-二苯基丙烯酸乙酯,α-氰基-β,β-二苯基丙烯酸异辛酯,α-甲酯基肉桂酸甲酯,α-氰基-β-甲基-对甲氧基肉桂酸甲酯,α-氰基-β-甲基-对甲氧基肉桂酸丁酯,α-甲酯基-对甲氧基肉桂酸甲酯和N-(β-甲酯基-β-氰基乙烯基)-2-甲基二氢吲哚。
2.5镍化合物类,例如2,2′-硫代-双-[4-(1,1,3,3-四甲基-丁基)苯酚]的镍配合物,如1∶1或1∶2配合比,有或没有附加的配位体如正丁基胺,三乙醇胺或N-环己基二乙醇胺,二丁基二硫代氨基甲酸镍,4-羟基-3,5-二叔丁基苄基膦酸的单烷基酯(例如甲酯或乙酯)类的镍盐,酮肟例如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物类,1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物,有或没有附加的配位体。
2.6空间位阻胺;例如癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯,琥珀酸双(2,2,6,6-四甲基-4-哌啶基)酯,癸二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯,癸二酸双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)酯,双(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯,1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性式环状缩合物,次氮基三乙酸三(2,2,6,6-四甲基-4-哌啶基)酯,1,2,3,4-丁烷四羧酸四(2,2,6,6-四甲基-4-哌啶基)酯,1,1′-(1,2-亚乙基)双(3,3,5,5-四甲基哌嗪酮),4-苯甲酰基-2,2,6,6-四甲基哌啶,4-硬脂酰氧基-2,2,6,6-四甲基哌啶,2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸双(1,2,2,6,6-五甲基哌啶基)酯,3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,癸二酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯,琥珀酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯,N,N′-双-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的线性或环状缩合物,2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物,2-氯-4,6-二(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物,8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮,3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮,4-十六烷氧基-和4-硬脂酰氧基-2,2,6,6-四甲基哌啶的混合物,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物,1,2-双(3-氨基-丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪的缩合物,以及4-丁基氨基-2,2,6,6-四甲基哌啶(CAS登记号[136504-96-6]);1,6-己二胺和2,4,6-三氯-1,3,5-三嗪以及N,N-二丁胺和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS登记号[192268-64-7]);N-(2,2,6,6-四甲基-4-哌啶基)正十二烷基琥珀酰亚胺,N-(1,2,2,6,6-五甲基-4-哌啶基)正十二烷基琥珀酰亚胺,2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺[4.5]癸烷,7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷和表氯醇的反应产物,1,1-双(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯,N,N’-双甲酰基-N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺,4-甲氧基-亚甲基-丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯,聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷,马来酸酐-α-烯烃共聚物与2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物。
2.7草酰胺类,例如4,4′-二辛氧基N,N′-草酰二苯胺,2,2′-二乙氧基N,N’-草酰二苯胺,2,2′-二辛氧基-5,5’-二叔丁氧基N,N’-草酰二苯胺(2,2’-dioctyloxy-5,5’-di-tert-butoxanilide),2,2’-二(十二烷氧基)-5,5’-二叔丁氧基N,N’-草酰二苯胺(2,2’-didodecyloxy-5,5’-di-tert-butoxanilide),2-乙氧基-2′-乙基N,N’-草酰二苯胺,N,N′-双(3-二甲氨基丙基)草酰胺,2-乙氧基-5-叔丁基-2′-乙氧基N,N’-草酰二苯胺(2-ethoxy-5-tert-butyl-2’-ethoxanilide)和它与2-乙氧基-2′-乙基-5,4′-二叔丁氧基N,N’-草酰二苯胺(2-ethoxy-2’-ethy1-5,4’-di-tert-butoxanilide)的混合物以及邻-和对-甲氧基双取代的N,N’-草酰二苯胺类的混合物和邻-和对-乙氧基-二取代的N,N’草酰二苯胺类的混合物。
3.金属减活剂类,例如N,N′-二苯基草酰胺,N-水杨醛-N′-水杨酰基肼,N,N′-双(水杨酰基)肼,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼,3-水杨酰基氨基-1,2,4-三唑,双(亚苄基)草酰二肼,N,N’-草酰二苯胺,间苯二甲酰二肼,癸二酰双(苯基肼),N,N′-二乙酰基己二酰二肼,N,N′-双(水杨酰基)草酰二肼,N,N′-双(水杨酰基)硫代丙酰基二肼。
4.亚磷酸酯类和亚膦酸酯类,例如亚磷酸三苯酯,亚磷酸二苯基烷基酯,亚磷酸苯基二烷基酯,亚磷酸三(壬基苯基)酯,亚磷酸三月桂基酯,亚磷酸三(十八烷基)酯,二亚磷酸二硬脂基季戊四醇酯,亚磷酸三(2,4-二叔丁基苯基)酯,二亚磷酸二异癸基季戊四醇酯,二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯,二亚磷酸双(2,4-二枯基苯基)季戊四醇酯,二亚磷酸双(2,6-二叔丁基-4-甲基苯基)-季戊四醇酯,二亚磷酸二异癸基氧基季戊四醇酯,二亚磷酸双(2,4-二叔丁基-6-甲基苯基)季戊四醇酯,二亚磷酸双(2,4,6-三叔丁基苯基)季戊四醇酯,三亚磷酸三硬脂基山梨糖醇酯,二膦酸四(2,4-二叔丁基苯基)4,4′-亚联苯基酯,6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-dioxaphosphocin,亚磷酸双(2,4-二叔丁基-6-甲基苯基)甲基酯,亚磷酸双(2,4-二叔丁基-6-甲基苯基)乙基酯,6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-次氮基[三乙基三(3,3’,5,5’-四叔丁基-1,1’-二苯基-2,2’-二基)亚磷酸酯],亚磷酸2-乙基己基(3,3’,5,5’-四叔丁基-1,1’-二苯基-2,2’-二基)酯,5-丁基-5-乙基-2-(2,4,6-三叔丁基苯氧基)-1,3,2-dioxaphophirane。
下列的亚磷酸酯是尤其优选的:
亚磷酸三(2,4-二叔丁基苯基)酯(Irgafos_168,Ciba-Geigy),亚磷酸三(壬基苯基)酯,
5.羟基胺类,例如N,N-二苄基羟基胺,N,N-二乙基羟基胺,N,N-二辛基羟基胺,N,N-二月桂基羟基胺,N,N-二(十四烷基)羟基胺,N,N-二(十六烷基)羟基胺,N,N-二(十八烷基)羟基胺,N-十六烷基-N-十八烷基羟基胺,N-十七烷基-N-十八烷基羟基胺,从氢化牛胺得到的N,N-二烷基羟基胺。
6.硝酮类,例如N-苄基-α-苯基-硝酮,N-乙基-α-甲基-硝酮,N-辛基-α-庚基-硝酮,N-月桂基-α-十一烷基-硝酮,N-十四烷基-α-十三烷基-硝酮,N-十六烷基-α-十五烷基-硝酮,N-十八烷基-α-十七烷基-硝酮,N-十六烷基-α-十七烷基-硝酮,N-十八烷基-α-十五烷基-硝酮,N-十七烷基-α-十七烷基-硝酮,N-十八烷基-α-十六烷基-硝酮,从氢化牛胺衍生而来的N,N-二烷基羟基胺获得的硝酮。
7.硫代协合剂,例如硫代二丙酸二月桂基酯或硫代二丙酸二硬脂基酯。
8.过氧化物清除剂,例如β-硫代二丙酸的酯类,例如月桂基、硬脂基、十四烷基或十三烷基酯类,巯基苯并咪唑或2-巯基苯并咪唑的锌盐,二丁基二硫代氨基甲酸锌,二(十八烷基)二硫化物,四(β-十二烷基巯基)丙酸季戊四醇酯。
9.聚酰胺稳定剂,例如铜盐与碘化物和/或磷化合物的混合物,和二价锰的盐。
10.碱性助稳定剂,例如三聚氰胺,聚乙烯基吡咯烷酮,双氰胺,三烯丙基氰脲酸酯,脲衍生物,肼衍生物,胺类,聚酰胺类,聚氨酯类,高级脂肪酸的碱金属盐和碱土金属盐,例如硬脂酸钙,硬脂酸锌,二十二烷酸镁,硬脂酸镁,蓖麻酸钠和棕榈酸钾,邻苯二酚锑或邻苯二酚锌。
11.成核剂类,例如,无机物质,如滑石,金属氧化物类如二氧化钛或氧化镁,磷酸盐、碳酸盐或硫酸盐,优选碱土金属的盐;有机化合物如单或多羧酸类和它们的盐类,例如4-叔丁基苯甲酸,己二酸,二苯基乙酸,琥珀酸钠或苯甲酸钠;聚合化合物如离子共聚物(“离子交联聚合物”)特别优选的是1,3:2,4-双(3’,4’-二甲基亚苄基)山梨醇,1,3:2,4-二(对甲基-二亚苄基)山梨醇,和1,3:2,4-二(亚苄基)山梨醇。
12.料和增强剂,例如碳酸钙,硅酸盐,玻璃纤维,玻璃球,石棉,滑石,高岭土,云母,硫酸钡,金属氧化物和氢氧化物,炭黑,石墨,木粉和其它天然产物的粉末或纤维,合成纤维。
13.其它添加剂,例如增塑剂,润滑剂,乳化剂,颜料,流变添加剂,催化剂,流动控制剂,荧光增白剂,阻燃剂,抗静电剂和发泡剂。
14.苯并呋喃酮类和二氢吲哚酮类,例如在US-A-4,325,863,US-A-4,338,244,US-A-5,175,312,US-A-5,216,052,US-A-5,252,643,DE-A-4,316,611,DE-A-4,316,622,DE-A-4,316,876,EP-A-0589839或EP-A-0591102中公开的那些,或3-[4-(2-乙酰氧基乙氧基)苯基]-5,7-二叔丁基-苯并呋喃-2-酮,5,7-二叔丁基-3-[4-(2-硬脂酰氧基乙氧基)苯基]苯并呋喃-2-酮,3,3′-双[5,7-二叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮],5,7-二叔丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮,3-(4-乙酰氧基-3,5-二甲基苯基)-5,7-二叔丁基-苯并呋喃-2-酮,3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二叔丁基-苯并呋喃-2-酮,3-(3,4-二甲基苯基)-5,7-二叔丁基-苯并呋喃-2-酮,3-(2,3-二甲基苯基)-5,7-二叔丁基-苯并呋喃-2-酮。
如果合适,普通的添加剂适当地以基于所要稳定的材料至多10重量%,例如0.1-10重量%,尤其0.2-5重量%的量使用。
可添加除酸剂,尤其为了改进与杀虫剂接触的农用材料例如棚膜的寿命。起到除酸剂作用的组分包括金属氧化物和/或氢氧化物,例如锌、镁、铝、钙的氧化物或氢氧化物,它们的混合盐,以及水滑石或沸石,例如在GB-A-2300192,2页2行到4页22行中描述的。
本发明的薄壁的制品,尤其透明聚烯烃农膜,用作选择性UV过滤材,用于增强植物和农作物生长而同时抑制微生物的所不希望的繁殖。这些微生物所需要的中或远UV区域的光(例如200-360纳米,尤其300-340纳米)被有效遮蔽。同时,益虫如蜜蜂和大黄蜂的活性没有受影响。
优选地,本发明的透明聚烯烃、聚酯或聚酰胺制品还包括位阻胺作为另外的稳定剂,为的是获得基材的最佳光稳定性。位阻胺的含量通常是聚烯烃、聚酯或聚酰胺的0.01-6重量%,位阻胺:羟苯基三嗪UV吸收剂的重量比优选是2∶1到20∶1。
包含在本发明的聚烯烃,聚酯或聚酰胺制品中的位阻胺的例子是在以上清单(2.6项)中给出的那些。
更优选的位阻胺类包括下面的化合物:
癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯;
癸二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯;
1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶和丁二酸的缩合物(CAS-No.65447-77-0);
N,N’,N”,N_-四(4,6-双(丁基-(N-甲基-2,2,6,6-四甲基哌啶-4-基)氨基)三嗪-2-基)-4,7-二氮杂癸烷-1,10-二胺(CAS-No.106990-43-6);
(Chimassorb_2020,CAS No.192268-64-7),
其中n主要在3-5范围内;或这些化合物的混合物。
用属于羟基胺醚类型的位阻胺获得了最佳结果。位阻羟基胺醚主要是含有一个或多个下式官能团的哌啶衍生物
其中R和R′独立地是氢或甲基,和至少氧原子的化学键和任选的其它化学键连接于有机残基,而剩余部分用氢饱和;或全部3个化学键连接于有机残基。这类化合物的例子尤其描述在US专利No.5204473,5216156,或GB-A-2347928中。
最优选的羟胺醚的例子是通式(1g-1)的化合物:
其中指数n在1-15范围内,尤其在3-9范围内;R12是C2-C12亚烷基,C4-C12亚链烯基,C5-C7亚环烷基,C5-C7亚环烷基-二(C1-C4亚烷基),C1-C4亚烷基二(C5-C7亚环烷基),亚苯基二(C1-C4亚烷基)或被1,4-哌啶二基、-O-或>N-X1插入的C4-C12亚烷基,其中X1是C1-C12酰基或(C1-C12烷氧基)羰基或具有以下给出的R14的定义中的一个,但氢除外;或R12是通式(Ib′)或(Ic′)的基团;
其中m是2或3,
X2是C1-C18烷基,未被取代或被1、2或3个C1-C4烷基取代的C5-C12环烷基;未被取代或被1、2或3个C1-C4烷基或C1-C4烷氧基取代的苯基;在苯基上未被取代或被1、2或3个C1-C4烷基取代的C7-C9苯基烷基;和
基团X3彼此独立地是C2-C12亚烷基;
基团B彼此独立地是Cl,-OR13,-N(R14)(R15)或通式(IIId)的基团;
R13,R14和R15,它们可以相同或不同,是氢,C1-C18烷基,未取代或被1、2或3个C1-C4烷基取代的C5-C12环烷基;C3-C18链烯基,未取代或被1、2或3个C1-C4烷基或C1-C4烷氧基取代的苯基;未取代或在苯基上被1、2或3个C1-C4烷基取代的C7-C9苯基烷基;四氢化糠基或在2、3或4位上被-OH、C1-C8烷氧基、二(C1-C4烷基)氨基或下式(Ie′)的基团取代的C2-C4烷基;
其中Y是-O-,-CH2-,-CH2CH2-或>N-CH3,,
或-N(R14)(R15)另外是式(Ie′)的基团;
X是-O-或>N-R16;
R16是氢,C1-C18烷基,C3-C18链烯基,未取代或被1、2或3个C1-C4烷基取代的C5-C12环烷基;未取代或在苯基上被1、2或3个C1-C4烷基取代的C7-C9苯基烷基;四氢化糠基,通式(IIIf)的基团,
或在2、3或4位上被-OH、C1-C8烷氧基,二(C1-C4烷基)氨基或通式(Ie′)的基团取代的C2-C4烷基;
R11具有对于R16给出的意义中的一个。
在这些化合物中,键接于三嗪残基的端基能够例如是基团B或-N(R11)-R12-B,如氯或基团
键接于二氨基的端基能够例如是氢或二-B-取代的三嗪基,如基团
也可以由例如-OH或氨基取代连接于三嗪的氯。合适的氨基典型地是:吡咯烷-1-基,吗啉子基,-NH2,-N(C1-C9烷基)2和-NY′(C1-C8烷基),
其中Y′是氢或下式的基团
在以上所示的低聚和聚合化合物中,烷基的例子是甲基,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,N-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,十三烷基,十四烷基,十五烷基,十六烷基,十七烷基,十八烷基,二十烷基和廿二烷基;
环烷基的例子是环戊基,环己基,环庚基和环辛基;
C7-C9苯基烷基的例子是苄基;和
亚烷基的例子是亚乙基,亚丙基,三亚甲基,四亚甲基,五亚甲基,2,2-二甲基三亚甲基,六亚甲基,三甲基六亚甲基,八亚甲基和十亚甲基。
有利地在本发明聚合物制品中使用的位阻胺醚的另一实例是下式的化合物
通式(1g-1)的高度有效化合物的例子是通式(1g-2)的化合物:
其中n′是大约3(GB-A-2334717的实施例2,CAS#247243-62-5,它是嵌段低聚物Chimassorb_2020 CAS#192268-64-7的NO-正丙基衍生物,Ciba Specialty Chemicals Corp.)。
本发明的添加剂和任选的其它组分可单独或作为混合物加入到聚合物材料中。如果需要,各组分能够在引入聚合物之前相互以熔融状态进行混合(熔体混合)。
本发明的添加剂和任选的其它添加剂在聚合物中的引入可通过已知方法来进行,如以粉末形式干混,或以溶液或悬浮液形式湿混。本发明的添加剂和任选的其它添加剂例如可在模塑之前或之后引入或通过将溶解或分散的添加剂或添加剂混合物施加到聚合物材料中来引入,可以有或没有后续的溶剂蒸发。它们可直接加入到加工设备(例如挤出机,密闭式混合机等)中,形式可以是例如干混物或粉末或溶液或熔体。
该引入能够在装有搅拌器的任何可加热的容器中进行,例如在密闭装置诸如捏和机,混合器或搅拌容器中进行。该引入优选在挤出机中或在捏合机中进行。不管在惰性气氛中还是在氧存在下进行加工都不是关键的。
本发明的添加剂和任选的其它添加剂也可以以母料形式加入到聚合物中,该母料含有浓度为例如大约2.5%到大约25重量%的组分;在该操作中,聚合物能够以粉末、粒料、溶液、悬浮液形式或以胶乳形式使用。
附图说明
图1:在低分子量HALS H-2(癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯)存在下在PP流延薄膜(0.1mm厚)中添加羟苯基-三嗪UV吸收剂化合物(j)的效果。T0.1=达到0.1羰基吸收的曝露时间。
图2:在聚合HALS H-3(CAS-No.65447-77-0,白色圆环),聚合HALS H-4(白色方块)以及1份H-3与1份H-4(填充的圆环)的掺混物存在下,在PP流延薄膜(0.1mm厚度)中添加羟苯基-三嗪UV吸收剂化合物(j)的效果。T0.1=达到0.1羰基吸收的曝露时间。
图3:在非聚合物高分子量HALS H-5存在下在PP流延薄膜(0.1mm厚)中添加羟苯基-三嗪UV吸收剂化合物j的效果。T0.1=达到0.1羰基吸收的曝露时间。
图4:在0.1%聚合HALS H-3存在下在PP带材(50微米厚)中添加羟苯基三嗪UV吸收剂(化合物j)的效果。E50=至50%保留抗张强度所需要的能量。
具体实施方式
下面的实施例用于进一步说明本发明,但不构成任何限制。份和百分数在这里以重量计;提及室温的实施例是指其采用在20-25℃范围内的温度。对于溶剂混合物如用于色谱的那些,份数由体积表示。使用这些定义,除非另有规定。
使用了下面的缩写:
m.p. 熔点或熔化范围
NMR 核磁共振
Tg 玻璃化转变温度;
h: 小时。
羟苯基三嗪UV吸收剂的制备
2,4-双-联苯基-6-[2-羟基-4-(2-乙基-己氧基)苯基]-1,3,5-三嗪的合成
将2,4-双-联苯基-6-[2,4-二羟苯基]-1,3,5-三嗪(11.2g,0.0227mol)在二甲基甲酰胺(30ml)中的黄色悬浮液在氮气氛围中于70℃下加热,直至形成透明的棕色溶液为止。添加无水碳酸钾(3.77g,0.0227mol),该棕色悬浮液在80℃下加热30分钟。经过30分钟滴加2-乙基己基溴(5.70g,0.0295mol),在此之后,将悬浮液在110℃下再加热3小时。过滤出沉淀的盐,滤液被冷却至0℃。添加甲醇(20ml),通过过滤分出沉淀的产物。在真空干燥之后,获得了2,4-双-联苯基-6-[2-羟基-4-(2-乙基己氧基-苯基]-1,3,5-三嗪(12.8g),mp70℃。
h)在以上制备中,当析出物2,4-双-联苯基-6-[2,4-二羟苯基]-1,3,5-三嗪被等量的2,4-双(4-甲氧苯基)-6-[2,4-二羟苯基)-1,3,5-三嗪代替时,获得下式的mp为105℃的化合物(h)
当使用相应量的其它烷基溴或亚烷基二溴重复以上反应(a)时,获得了在下表中所示的化合物。
实施例 | R-1 | Mp:℃ |
b) | CH(CH3)-(CH2)9-CH3 | 油 |
c) | n-C6H13 | 178 |
d) | n-C8H17 | 160 |
e) | n-C12H25 | 146 |
实施例 | X | Mp:℃ |
f) | -(CH2)10- | >250 |
g) | -(CH2)12- | >250 |
当使用合适的亚烷基二溴或被-CO-O-D-O-CO-或氧插入的亚烷基二溴,或脂族C15-C26二酰氯或溴时,获得了其中X是C13-C24亚烷基,(C1-C18亚烷基)-CO-O-D-O-CO-(C1-C18亚烷基),CO-(C13-C24亚烷基)-CO;被氧插入的C3-C24亚烷基,尤其(C1-C3亚烷基)-O-(C1-C3亚烷基)的对应化合物。
I)下式化合物的制备:
按照与WO96/28431的实施例16类似的方式,从以下起始原料获得白色粉末物:4-(4,6-双-联苯基-4-基-(1,3,5)三嗪-2-基)-苯-1,3-二醇和烯丙基溴。
1H NMR(300MHz,CDCl3):δ=13.3(s,1H),8.7-6.2(芳族信号,21H),6.1(m,1H),5.3(m,2H),4.3(m,2H)。
m)下式低聚物的制备:
将30g(0.056mol)实施例(I)的化合物和30.2g(0.320mol)的降冰片烯和42.3g(0.320mol)的双环戊二烯和0.49g(0.6mmol)的催化剂双(三环戊基膦)二氯(3-甲基-2-亚丁烯基)合钌(APT Cat ASMC 716)加入到300ml的甲苯中。该混合物在30℃下反应24小时。在真空下浓缩该溶液,获得浅棕色固体物。
目测熔化范围:168-180℃;Mn:2216;Mw:4663;PDI:2.10;
元素分析:
%C | %H | %N | |
理论值实测值 | 87.585.8 | 8.48.6 | 2.32.1 |
n)下式氢化低聚物的制备:
向92g(0.050mol)的实施例(m)的低聚物在300ml二甲苯中的溶液添加1.0g的铂/碳(10%重量/重量)。该混合物被倾倒在高压釜中并在65巴(PH2)和105℃下氢化24小时。通过在80-90℃下添加10g的Tonsyll_414 FF并在剧烈搅拌下保持2小时,以除去催化剂以提纯氢化混合物。在10g的Tonsil的填料上过滤之后,真空浓缩所过滤出的黄色溶液,得到浅黄固体。
目测熔化范围:55-68℃;Mn:2197;Mw:4347;PDI:1.98;ε(290nm,甲苯):34574;
元素分析:
%C | %H | %N | |
理论值实测值 | 85.884.7 | 10.210.2 | 2.22.0 |
应用实施例
在一些应用实施例中,使用下面的位阻胺(HALS):
化合物 结构式/化学名称
H-2 癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯;
H-3 1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶和
丁二酸(CAS-No.65447-77-0)的缩合物
H-4
H-5 N,N’,N”,N_-四(4,6-双(丁基-(N-甲基-2,2,6,6-
四甲基哌啶-4-基)氨基)三嗪-2-基)-4,7-二
氮杂癸烷-1,10-二胺(CAS-No.106990-43-
6)。
实施例1羟苯基三嗪化合物(a)与化合物(1g-2)的结合。
为了评估羟苯基三嗪化合物(a)在与商购热塑性材料混合时的UV吸收剂特性,制备薄的低密度聚乙烯(LDPE)膜,作为典型的配方,含有0.15重量%的以上化合物(a)和0.70重量%的位阻胺醚(1g-2),在农业应用的高要求环境中用作聚合物体系的光稳定剂。为此,将适当称取量的化合物与磨细的LDPE(Polimeri,Europa,由Enichem提供,Milano,意大利)(以0.921g/cm3的密度和0.6的熔体流动指数(190℃/2.16kg)为特征)在涡轮式混合器中混合。该混合物在OMC_双螺杆挤出机中在200℃的最高温度下挤出。如此获得的粒料在实验室规模的Formac_吹塑机中在210℃的最高温度下吹塑,得到150微米厚度的膜。
利用装有RSA-PE-20 Labsphere_积算球的Perkin-Elmerlambda_20分光光度计,在200-800nm范围内记录这样获得的膜的UV-Vis谱图。在0.15%填充量下,化合物(a)赋予膜以强UV吸收特征,透射率值在290和360纳米之间小于10%,在300和340纳米之间小于1%。在Atlas Ci 65 Xenon Arc耐候试验仪(Weather-O-meter_)(WOM,63℃黑板温度,连续干燥周期,根据ASTM G 26-96)中将膜样品曝露于UV光来表明化合物(a)的光稳定性。在WOM曝照1500小时后,由该膜显示的最低透射率在320纳米下仍然在1%左右。
化合物(a)在LDPE膜中完全相容;在膜于室温下贮存6000小时后没有观察到模糊现象。在将膜在60℃烘箱中保持同样长的时间之后观察到同样的行为。在烘箱中暴露了同样的时间之后,在UV-Vis吸收谱中没有观察到显著的变化,意味着没有因为高温而使添加剂损失。
继续进行在这一实施例中描述的配制料的WOM曝露操作,以评价含有化合物(a)的聚合物的光稳定性。样品还经受自然老化和用杀虫剂处理,以评估对在农业中使用的化学品的抵抗力。
实施例2:羟苯基三嗪化合物(c)在聚乙烯农膜中用作UV过滤剂
为了制备薄的LDPE膜和评价由添加剂赋予的光谱特征和它的持久性,化合物(c)与LDPE粒料(Riblene FF 29,由Polimeri Europa提供,Milano,意大利)在涡轮式混合器中混合,以获得含有0.15重量%添加剂的配制料,其中该粒料以0.921g/cm3的密度和0.6的熔体流动指数(190℃/2.16kg)为特征。该混合物在OMC双螺杆挤出机中在200℃的最高温度下挤出。如此获得的粒料在实验室规模的Formac吹塑机中在210℃的最高温度下吹塑,得到150微米厚度的膜。利用装有RSA-PE-20 Labsphere积算球的Perkin-Elmer Lambda 20分光光度计,在200-800nm范围内记录UV-Vis谱图。
结果:该膜显示出在280-360纳米范围内的强吸收带。尤其,透射率在以上提及的范围内低于20%和在295-345纳米范围内低于5%。
为了测试添加剂在曝露于光之后的光稳定性,将一部分的膜在Atlas耐候试验仪(Weather-O-meter)(WOM),Ci65A型(按照ASTMG26-96,辐照度0.35W/m2,黑板温度63±3℃)中曝照。在曝照1000小时之后,该膜仍然显示出在280和360纳米之间低于40%和在295和345纳米之间低于25%的透射率。
实施例3
按照实施例2中所述,制备含有0.15重量%的化合物(d)的膜。该膜显示出在280-360纳米范围内的强吸收带。尤其,透射率在以上提及的范围内低于20%和在295-345纳米范围内低于5%。
在WOM中曝照1000小时(有关细节参见实施例2)后,该膜仍然保持了以上所述的光谱特征。
另一部分的膜也在60℃的强制空气循环烘箱中曝露,以评价在膜中添加剂的热持久性。在1000小时的曝照之后,膜仍然保持了初始光谱特征。
实施例4
按照实施例2中所述,制备含有0.15重量%的化合物(b)的膜。该膜显示出在280-360纳米范围内的强吸收带。尤其,透射率在以上提及的范围内是低于20%和在295-345纳米范围内是低于5%。
在WOM中曝照1000小时(有关细节参见实施例2)后,该膜仍然保持了以上所述的光谱特征。
实施例5
按照实施例2中所述,制备含有0.15重量%的化合物(g)的膜。该膜显示出在280-360纳米范围内的强吸收带。尤其,透射率在以上提及的范围内是低于20%和在295-345纳米范围内是低于5%。
在WOM中曝照1000小时之后(细节参见实施例2),该膜仍然显示出在280和360纳米之间低于25%和在295和345纳米之间低于10%的透射率。
另一部分的膜也在60℃的烘箱中曝露。在1000小时的曝照之后,膜保持了原吸收量的大约75%。
实施例6:
按照实施例2中所述,制备含有0.15重量%的化合物(f)的膜。该膜显示出在280-360纳米范围内的强吸收带。尤其,透射率在以上提及的范围内是低于20%和在295-345纳米范围内是低于5%。
在WOM中曝照1000小时之后(细节参见实施例2),该膜仍然显示出在280和360纳米之间低于25%和在295和345纳米之间低于15%的透射率。
实施例7:聚丙烯(PP)流延薄膜的光稳定化
将100份聚丙烯粉料(熔体流动指数3.8g/10分钟,230℃/2160g)在滚筒式混合机中与0.05份四-3-(3,5-二叔丁基-4-羟苯基)-丙酸季戊四醇酯,0.05份的亚磷酸三(2,4-二叔丁基苯基)酯,0.1份硬脂酸钙,0.1份HALS和在附图中所示的用量的UV吸收剂(化合物j)掺混。然后该共混物在挤出机中在180-220℃的温度下配混。经过挤出和造粒所获得的粒料在装有平片模头的第二台挤出机中在220-260℃下转变成膜。从这些0.11mm膜中裁切出60×25mm的样品并在耐候试验仪Ci65(黑板温度63℃±2℃,没有喷射水)中曝照。
这些样品定期从曝照装置中取出和用红外分光光度计测量它们的羰基含量。对应于形成0.1的羰基吸收的曝光时间是光稳定剂的稳定效果的量度。所获得的值被描绘在图1,图2和图3中。使用的HALS(各0.1份/每100份PP)见附图说明。
曲线显示,少量的羟苯基三嗪UV吸收剂就已经达到了由HALS所能实现的UV稳定性的显著改进。
实施例8:聚丙烯带的光稳定化
将100份聚丙烯粉料(熔体流动指数3.5g/10分钟,230℃/2160g)在滚筒式混合机中与0.05份四-3-(3,5-二叔丁基-4-羟苯基)-丙酸季戊四醇酯,0.05份亚磷酸三(2,4-二叔丁基苯基)酯,0.1份硬脂酸钙,0.1%聚合HALS H-3(1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶和丁二酸(CAS-No.65447-77-0)的缩合物)和图4中所示用量的光稳定剂化合物(j)进行混合。然后该共混物在挤出机中在180-220℃的温度下配混。经过挤出和造粒所获得的粒料在装有平片模头的第二台挤出机中在220-260℃下转变成膜。将该膜切成丝带,经过拉伸达到1∶6的拉伸比。用该程序获得的带材最终是50微米厚度和2.5mm宽度。
该带材在没有张力的情况下被安置在样品夹持器中并在佛罗里达州(45°南,直接,大约140kLy/年)经受自然老化。定期测定曝照的带材的抗张强度。对应于初始抗张强度的50%的损失的接收能量(kLy)是光稳定剂的稳定效果的量度。用聚合HALS和羟苯基三嗪UV吸收剂获得的值被描绘图4中。
该结果显示,在厚度不到实施例7中所用PP膜的一半的PP带材中UV吸收剂对光稳定性的贡献也是突出的。
实施例9:聚丙烯带材的光稳定化
将100份聚丙烯粉料(熔体流动指数3.5g/10分钟,230℃/2160g)在滚筒式混合机中与0.05份四-3-(3,5-二叔丁基-4-羟苯基)-丙酸季戊四醇酯,0.05份的亚磷酸三(2,4-二叔丁基苯基)酯,0.1份硬脂酸钙和在下面的表中所示的用量的光稳定剂掺混。然后该共混物在挤出机中在180-220℃的温度下配混。经过挤出和造粒所获得的粒料在装有平片模头的第二台挤出机中在220-260℃下转变成膜。将该膜切成丝带,经过拉伸达到1∶6的拉伸比。用该程序获得的带材最终是50微米厚度和2.5mm宽度。
带材在没有张力的情况下被安放在样品夹持器中并在耐候试验仪Ci65(黑板温度63+2℃,没有喷射水)曝照。定期测定曝照的带材的抗张强度。对应于初始抗张强度的50%的损失的曝光时间(T50)是光稳定剂的稳定效果的量度。
所获得的值总结在下表中
表:各种UV吸收剂类型对HALS在PP带材中的性能的影响。
HALS | UV吸收剂 | T50(h) |
无 | 无 | 530 |
0.1%H-3 | 无 | 2150 |
0.1%H-3 | 0.1%V-1 | 2500 |
0.1%H-3 | 0.1%V-2 | 2700 |
0.1%H-3 | 0.1%化合物j | 3800 |
0.1%H-4 | 无 | 3000 |
0.1%H-4 | 0.1%V-2 | 2900 |
0.1%H-4 | 0.1%化合物j | 4150 |
化合物V-1是2-(2’-羟基-3’-叔丁基-5’-甲基苯基)-5-氯苯并三唑。
化合物V-2具有下式
数据显示,羟苯基三嗪UV吸收剂(化合物j)对带材的光稳定性的贡献是显著的,而苯并三唑或二苯甲酮UV吸收剂(V-1和V-2)的贡献则保持在较低的水平或没有检测出来。
实施例10:化合物(m)在LDPE中的吸收谱带和持久性:
按照实施例2中所述,未添加HALS来制备薄的低密度聚乙烯(LDPE)膜。它们是150μm厚度和含有0.5%的化合物(m)。按照实施例2中所述记录UV-Vis谱图。该膜在280-360纳米范围内显示出强吸收。在290-350纳米范围内检测到低于3%的透射率。
使膜在强制空气循环烘箱中于60℃曝露之后测定聚合物在LDPE膜中的持久性并按照实施例3中所述进行评价。在60℃下经过3000小时后,没有观察到最大吸光率值的下降。
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CN110446749A (zh) * | 2017-03-28 | 2019-11-12 | 巴斯夫欧洲公司 | 光稳定剂混合物 |
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