CN101379123B - 空间位阻仲胺在旋转模塑方法中作为加工添加剂的用途 - Google Patents
空间位阻仲胺在旋转模塑方法中作为加工添加剂的用途 Download PDFInfo
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- CN101379123B CN101379123B CN2007800040929A CN200780004092A CN101379123B CN 101379123 B CN101379123 B CN 101379123B CN 2007800040929 A CN2007800040929 A CN 2007800040929A CN 200780004092 A CN200780004092 A CN 200780004092A CN 101379123 B CN101379123 B CN 101379123B
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- Prior art keywords
- butyl
- sterically hindered
- phenyl
- hindered amines
- hydroxyl
- Prior art date
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- -1 amines compound Chemical class 0.000 claims description 93
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
- B29C41/06—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould about two or more axes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Moulding By Coating Moulds (AREA)
- Hydrogenated Pyridines (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
本发明涉及空间位阻仲胺在旋转模塑方法中作为加工添加剂的用途。这些添加剂提高了方法稳定性,因为它们在熔体加工步骤期间朝着更高的温度提供了更宽的温度范围。
Description
本发明涉及空间位阻仲胺(secondary sterically hindered amines)在旋转模塑方法中作为加工添加剂的用途。这些添加剂提高了方法稳定性,因为它们在熔体加工步骤期间朝着更高的温度提供了更宽的温度范围。
旋转模塑是一种高度通用的制造选择,其允许无限制的设计可能性,具有低生产成本的附加益处。
旋转模塑方法从优质模具开始,所述模具被放入具有一定负载、加热和冷却面积的模塑机中。
多个模具可以同时被放置在机器上。预测量的塑料树脂载入各个模具中,然后将模具移入烘箱中,其中它们缓慢地绕垂直轴和水平轴旋转。熔融树脂粘住热模具并且均匀地涂布每个表面。在冷却循环期间模具继续旋转,所以零件保持了均匀的壁厚。
一旦零件冷却,将它们从模具中取下。在该方法过程中,可以全部控制转速、加热和冷却时间。
相比于其它模塑方法,旋转模塑提供了设计优势。在合适设计的情况下,从数个部分装配的零件能够以一个零件的形式进行模塑,消除了昂贵的生产成本。
该方法还具有许多固有的设计强度,如一致的壁厚和结实的外棱角,其几乎没有应力。如果需要附加强度的话,可以将增强肋材设计到零件中。
旋转模塑使产品赋予了设计者的想象。设计者可以选择用于其应用的最佳材料,包括满足FDA要求的材料。可以规定有助于使得所述零件耐候、阻燃或不受天电干扰(static free)的添加剂。
并且因为零件借助热量和旋转形成,而不是借助压力,所述模具无需被设计为经受注塑的高压。
对于单件产品原型来说,当其用于大型生产过程时,因为重量轻的塑料代替了更重的、通常更昂贵的材料,这使得旋转模塑是有成本效率的,所以降低了产品转化的生产成本。
旋转模塑是通用的并且能够加工各种各样的形状和尺寸。通过任何其它方法,许多部件不能容易地被生产出来。典型的实例是用于燃料、水和化学处理的专用槽和容器,牲畜送料器,排水系统,饮食服务容器,仪表壳体,自动售货机,公路隔离物和路面划线机。其它应用领域是消费品,玩具和运输工具。旋转模塑方法的许多方面例如被R.J.Crawford和J.L.Throne在Rotational MoldingTechnology,Plastics Design Library,William Andrew Publishing,2001中进行了描述。
如上所述,在该方法过程中,可以全部控制转速、加热和冷却时间。到达空心模制品内部的空气的最高温度强有力地取决于加热时间。这种温度还被称为峰值内部空气温度(PIAT)。它与熔融树脂的温度有关。
峰值内部空气温度(PIAT)的观念以及施加太低或过高的PIAT的后果例如被M.C.Cramez等人在Proc.Instn Mech.Engrs.Vol.217PartB:J.of Engineering Manufacture,2003中进行了描述。
峰值内部空气温度可以影响模塑产品的最终性能。例如,如果温度变得过高,强烈变黄可能出现,此外,负面地影响了机械性能,例如,冲击强度显著地下降。如果温度保持太低,最终性能还可能受到负面影响,因为树脂没有被适当地熔融。换言之,仅仅存在小的用于获得期望的最终性能的温度范围。因此,特别令人关注的是加宽这种温度范围或加工范围,在上述范围内获得了几乎不变的机械性能。
Botkin等在以下文章中″An additive approach to cycle timereduction in rotational molding″(Rotational Molding by DesignConference,Society of Plastics Engineers,2004)已经证明通过使用专有的加工稳定剂,在保持良好的冲击强度条件下,PIAT可以朝着较低的温度移动。这相应于朝着较低的温度加宽加工范围。
令人惊讶地,现在已经发现当位阻仲胺化合物被添加到树脂制剂时,获得了朝更高温度的更宽的加工范围,但没有不利地影响模制品的颜色和机械性能。
因此,本发明的一个方面是空间位阻仲胺化合物作为加工添加剂在热塑性聚合物的旋转模塑方法中朝更高的峰值内部空气温度扩大加工范围的用途。
在加工范围下,要理解的是如通过峰值内部空气方法(PIAT)测量的温度范围,在所述温度范围内,模制品的机械性能和/或颜色保持基本上相同。要测量的特别合适的机械性能是冲击强度,例如在低温。在这方面低温是指0°至-50℃,特别地,-20℃至-40℃。
例如,空间位阻胺是含通式(I)或(II)中至少一个基团的化合物
其中
*表示键
G是氢或甲基,和
G1和G2,彼此独立地是氢,甲基或者合起来是取代基=O。
例如,空间位阻胺是含通式(Ia)中至少一个基团的化合物。
空间位阻胺化合物是已知的并且广泛用作用于聚合物的热或光稳定剂。它们或者是市售可得的或者可以是例如按照以下文献中所述的进行制备:
US-A-5,679,733,US-A-3,640,928,US-A-4,198,334,US-A-5,204,473,US-A-4,619,958,US-A-4,110,306,US-A-4,110,334,US-A-4,689,416,US-A-4,408,051,SU-A-768,175(Derwent 88-138,751/20),US-A-5,049,604,US-A-4,769,457,US-A-4,356,307,US-A-4,619,956,US-A-5,182,390,GB-A-2,269,819,US-A-4,292,240,US-A-5,026,849,US-A-5,071,981,US-A-4,547,538,US-A-4,976,889,US-A-4,086,204,US-A-6,046,304,US-A-4,331,586,US-A-4,108,829,US-A-5,051,458,WO-A-94/12,544(Derwent94-177,274/22),DD-A-262,439(Derwent 89-122,983/17),US-A-4,857,595,US-A-4,529,760,US-A-4,477,615,CAS 136,504-96-6,US-A-4,233,412,US-A-4,340,534,WO-A-98/51,690和EP-A-1,803,
其公开内容作为参考引入。
优选的是以下商品化合物。
Chimassorb 2020Chimassorb 944Tinuvin 770和Tinuvin 783Cyasorb UV 3346Cyasorb UV 3581Dastib 845Dastib 1082Diacetam 5,Fero 806-XGoodrite 3034Goodrite 3150HALS IC-TAM,Hostavin N 20Hostavin N 24Hostavin N 30Hüls S-95ICI PA 500Lichtschutzstoff UV 31,Luchem HA-B 18Mark LA 55Mark LA 57Mark LA 67Mark LA 68Sanduvor 3050Sumilizer 61Sumilizer 70Suimisorb TM61UVASORB HA 88Uvinul 4049Uvinul 5050Uvasil 299Uvasil 125
这些化合物是市售可得的并且描述于以下文献中:
US-A-5,679,733,US-A-3,640,928,US-A-5,204,473,US-A-4,619,958,US-A-4,110,306,US-A-4,110,334,US-A-4,689,416,US-A-4,408,051,SU-A-768,175(Derwent 88-138,751/20),US-A-5,049,604,US-A-4,769,457,US-A-4,356,307,US-A-4,619,956,US-A-5,182,390,GB-A-2,269,819,US-A-4,292,240,US-A-5,026,849,US-A-5,071,981,US-A-4,547,538,US-A-4,976,889,US-A-4,086,204,US-A-6,046,304,US-A-4,331,586,US-A-4,108,829,US-A-5,051,458,WO-A-94/12,544(Derwent 94-177,274/22),DD-A-262,439(Derwent89-122,983/17),US-A-4,857,595,US-A-4,529,760,US-A-4,477,615(CAS 136,504-96-6),US-A-4,340,534,WO-A-98/51,690,EP-A-1,803,
其公开内容作为参考引入。
根据本发明的空间位阻胺化合物优选地以下述数量添加:0.01至5wt%,更优选地0.05至2wt%,最优选地0.1至1wt%,基于热塑性聚合物的重量。
例如,热塑性聚合物是聚烯烃、聚氯乙烯或聚酰胺。实例是在下文中给出。
1、单烯烃和二烯烃的聚合物,例如聚丙烯,聚异丁烯,聚丁-1-烯,聚-4-甲基戊-1-烯,聚乙烯基环己烷,聚异戊二烯或聚丁二烯,以及环烯如环戊烯或降冰片烯的聚合物,聚乙烯(其任选地可以是交联的),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),中密度聚乙烯(MDPE),低密度聚乙烯(LDPE),线型低密度聚乙烯(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,尤其通过下面的方法来制备:
a)自由基聚合反应(一般在高压和升温下)。
b)使用一般含有一种或一种以上的元素周期表的IVb,Vb,VIb或VIII族的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体,典型的可以是π键或σ键配位的氧根,卤素,醇根,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材上,通常固定在活性氯化镁、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中。该催化剂本身可用于聚合反应或另外可以使用活化剂,通常金属烷基化物,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),所述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菲利普类催化剂,印地安纳美孚油公司催化剂(Standard Oil Indiana),齐格勒(-纳塔)催化剂,TNZ(DuPont),茂金属或单一位点催化剂(SSC)。
2、在以上项1)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、单烯烃和二烯烃互相的共聚物,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,线型低密度聚乙烯(LLDPE)及其与低密度聚乙烯(LDPE)的混合物,丙烯/丁-1-烯共聚物,丙烯/异丁烯共聚物,乙烯/丁-1-烯共聚物,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,乙烯/乙烯基环己烷共聚物,乙烯/环烯共聚物(例如乙烯/降冰片烯如COC),乙烯/1-烯烃共聚物,其中1-烯烃就地生成;丙烯/丁二烯共聚物,异丁烯/异戊二烯共聚物,乙烯/乙烯基环己烯共聚物,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/乙酸乙烯酯共聚物或乙烯/丙烯酸共聚物和它们的盐类(离聚物类)以及乙烯与丙烯和二烯烃如己二烯、双环戊二烯或乙叉-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/一氧化碳共聚物和其与其它聚合物如聚酰胺的混合物。
4、由二胺和二羧酸和/或氨基羧酸或相应的内酰胺衍生而来的聚酰胺和共聚酰胺,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,以间-二甲苯二胺和己二酸为原料的芳族聚酰胺;从六亚甲基二胺和间苯二甲酸或/和对苯二甲酸制备的并且有或没有弹性体作为改性剂的聚酰胺,例如聚-2,4,4-三甲基亚己基对苯二甲酰二胺或聚间亚苯基间苯二甲酰二胺;还有上述聚酰胺与聚烯烃,烯烃共聚物,离聚物或化学键连接的或接枝的弹性体,或与聚醚类,如聚乙二醇、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)。
特别优选的是聚乙烯,优选地线型低密度聚乙烯(LLDPE)。
例如,在旋转模塑方法中的峰值内部空气温度范围朝更高温度被扩大至多10至50℃,优选地至多15至40℃。基准是没有添加空间位阻胺的情况。
优选地,峰值内部空气温度范围是210至250℃,更优选地215至250℃和最优选地220至250℃。
上述温度范围相应于优选的加工范围,在所述范围内,没有不利地影响制品的机械性能和/或颜色。
在本发明的特定的实施方案中,存在着另外的稳定剂,其选自UV-吸收剂、空间位阻胺,其不同于通式(I)或者(II)的那种、酚类抗氧化剂、亚磷酸酯或者亚膦酸酯(phosphonite)和苯并呋喃酮(benzofuranone)或者二氢吲哚酮(indolinone)。
上述添加剂的实例在下文中给出。
1.抗氧化剂
1.1、烷基化的单苯酚,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,在侧链中是直链或支链的壬基苯酚,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)苯酚和其混合物。
1.2、烷基硫基甲基苯酚,例如2,4-二辛基硫基甲基-6-叔丁基苯酚,2,4-二辛基硫基甲基-6-甲基苯酚,2,4-二辛基硫基甲基-6-乙基苯酚,2,6-二-十二烷基硫基甲基-4-壬基苯酚。
1.3、氢醌和烷基化氢醌,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-羟基茴香醚,3,5-二叔丁基-4-羟基茴香醚,硬脂酸3,5-二叔丁基-4-羟苯基酯,双(3,5-二叔丁基-4-羟苯基)己二酸酯。
1.4、生育酚,例如α-生育酚,β-生育酚,γ-生育酚,δ-生育酚和其混合物(维生素E)。
1.5、羟基化硫基二苯醚,例如2,2′-硫基双(6-叔丁基-4-甲基苯酚),2,2′-硫基双(4-辛基苯酚),4,4′-硫基双(6-叔丁基-3-甲基苯酚),4,4′-硫基双(6-叔丁基-2-甲基苯酚),4,4′-硫基双(3,6-二-仲戊基苯酚),4,4′-双(2,6-二甲基-4-羟苯基)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,乙二醇双[3,3-双(3′-叔丁基-4′-羟苯基)丁酸酯],双(3-叔丁基-4-羟基-5-甲基-苯基)双环戊二烯,双[2-(3′-叔丁基-2′-羟基-5′-甲苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯,1,1-双-(3,5-二甲基-2-羟苯基)丁烷,2,2-双(3,5-二叔丁基-4-羟苯基)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,十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯,十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯,三(3,5-二叔丁基-4-羟基苄基)胺,双(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫基对苯二甲酸酯,双(3,5-二叔丁基-4-羟基苄基)硫化物,异辛基-3,5-二叔丁基-4-羟基苄基巯基乙酸酯。
1.8、羟苄基化丙二酸酯类,例如双十八烷基-2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸酯,双十八烷基-2-(3-叔丁基-4-羟基-5-甲苄基)丙二酸酯,双十二烷基巯基乙基-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯,双[4-(1,1,3,3-四甲基丁基)苯基]-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯。
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)-2,4,6-三甲苯,1,4-双(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲苯,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-双环己基-4-羟基苄基)异氰脲酸酯。
1.11、苄基膦酸酯类,例如二甲基-2,5-二叔丁基-4-羟基苄基膦酸酯,二乙基-3,5-二叔丁基-4-羟基苄基膦酸酯,双十八烷基-3,5-二叔丁基-4-羟基苄基膦酸酯,双十八烷基-5-叔丁基-4-羟基-3-甲基苄基膦酸酯,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-羟苯基)氨基甲酸辛基酯。
1.13、β-(3,5-二叔丁基-4-羟苯基)丙酸的酯,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,正辛醇,异辛醇,十八醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫基二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫杂(thia-)十一烷醇,3-硫杂(thia-)十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.14、β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸的酯,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,正辛醇,异辛醇,十八醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫基二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫杂(thia-)十一烷醇,3-硫杂(thia-)十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂二环[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[5.5]十一烷。
1.15、β-(3,5-双环己基-4-羟苯基)丙酸的酯,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,辛醇,十八醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫基二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫杂(thia-)十一烷醇,3-硫杂(thia-)十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.16、3,5-二叔丁基-4-羟基苯基乙酸的酯类,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,辛醇,十八醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫基二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫杂(thia-)十一烷醇,3-硫杂(thia-)十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.17、β-(3,5-二叔丁基-4-羟苯基)丙酸的酰胺,例如N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)己二酰胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)丙二酰胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰)肼,N,N′-双[2-(3-[3,5-二叔丁基-4-羟苯基]丙酰氧基)乙基]草酰胺(NaugardXL-1,由Uniroyal供给)。
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-对苯二胺、N,N′-二-仲丁基-对苯二胺、N,N′-双(1,4-二甲基戊基)对苯二胺、N,N′-双(1-乙基-3-甲基戊基)对苯二胺、N,N′-双(1-甲基庚基)对苯二胺、N,N′-双环己基对苯二胺、N,N′-二苯对苯二胺、N,N′-双(2-萘基)对苯二胺、N-异丙基-N′-苯基-对苯二胺、N-(1,3-二甲基丁基)-N′-苯基-对苯二胺、N-(1-甲基庚基)-N′-苯基-对苯二胺、N-环己基-N′-苯基-对苯二胺、4-(对甲苯氨磺酰)二苯胺、N,N′-二甲基-N,N′-二-仲丁基-对苯二胺、二苯胺、N-烯丙基二苯胺、4-异丙氧基二苯胺、N-苯基-1-萘胺、N-(4-叔辛基苯基)-1-萘胺、N-苯基-2-萘胺、辛基化二苯胺、例如对,对′-二叔辛基二苯胺、4-正丁基氨基苯酚、4-丁酰基氨基苯酚、4-壬酰氨基苯酚、4-十二烷酰氨基苯酚、4-十八烷酰氨基苯酚、双(4-甲氧基苯基)胺、2,6-二叔丁基-4-二甲基氨基甲基苯酚、2,4′-二氨基二苯甲烷、4,4′-二氨基二苯甲烷、N,N,N′,N′-四甲基-4,4′-二氨基二苯甲烷、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)缩二胍、双[4-(1′,3′-二甲基丁基)苯基]胺、叔辛基化N-苯基-1-萘胺、单和二烷基化叔丁基/叔辛基二苯胺的混合物、单和二烷基化壬基二苯胺的混合物、单和二烷基化十二烷基二苯胺的混合物、单和二烷基化异丙基/异己基二苯胺的混合物、单和二烷基化叔丁基二苯胺的混合物、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。
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′-羟苯基)苯并三唑、2-(5′-叔丁基-2′-羟苯基)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′-羟苯基)苯并三唑、2-(3′,5′-双(α,α-二甲基苄基)-2′-羟苯基)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′-羟苯基]-2H-苯并三唑与聚乙二醇300的酯交换产物;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4-叔丁基-水杨酸苯酯,水杨酸苯酯,辛基苯基水杨酸酯,二苯甲酰间苯二酚,双(4-叔丁基苯甲酰)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-二苯基丙烯酸乙基酯,α-氰基-β,β-二苯基丙烯酸异辛基酯,α-甲氧羰基肉桂酸甲基酯,α-氰基-β-甲基-对甲氧基肉桂酸甲基酯,α-氰基-β-甲基-对甲氧基肉桂酸丁基酯,α-甲氧羰基-p-甲氧基肉桂酸甲基酯,N-(β-甲氧羰基-β-氰基乙烯基)-2-甲基二氢吲哚,新戊基四(α-氰基-β,β-二苯基丙烯酸酯。
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,例如双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、双(1,2,2,6,6-五甲基4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、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-羟基哌啶和丁二酸的缩合物、N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺和4-叔辛基氨基-2,6-二氯1,3,5-三嗪的线性或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、1,1′-(1,2-乙烷二基)-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、4-十八烷氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、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、双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺和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-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4-十八烷氧基-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)己二胺和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-1,3,5-三嗪以及4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(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、2-十一基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧-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-甲氧苯基)乙烯、N,N′-双甲酰基-N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺、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、2,4-双[N-(1-环己基氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁氨基]-6-(2-羟乙基)氨基-1,3,5-三嗪、1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2,2,6,6-四甲基哌啶、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、Sanduvor(Clariant;CAS登记号106917-31-1]、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、2,4-双[(1-环己基氧基-2,2,6,6-哌啶-4-基)丁氨基]-6-氯-s-三嗪与N,N′-双(3-氨基丙基)乙二胺)的反应产物、1,3,5-三(N-环己基-N-(2,2,6,6-四甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、1,3,5-三(N-环己基-N-(1,2,2,6,6-五甲基哌嗪-3-酮-4-基)氨基)-s-三嗪。
2.7.草酰胺,例如4,4′-二辛氧基草酰替苯胺、2,2′-二乙氧基草酰替苯胺、2,2’-二辛氧基-5,5′-二叔丁基草酰替苯胺(butoxanilide)、2,2′-双十二烷氧基-5,5′-二叔丁基草酰替苯胺(butoxanilide)、2-乙氧基2′-乙基草酰替苯胺、N,N′-双(3-二甲基氨基丙基)草酰胺、2-乙氧基5-叔丁基-2′-乙基草酰替苯胺(ethoxanilide)和其与2-乙氧基2′-乙基-5,4′-二叔丁基草酰替苯胺的混合物、邻和对甲氧基二取代的草酰替苯胺的混合物和邻和对乙氧基二取代的草酰替苯胺的混合物。
2.8.2-(2-羟苯基)-1,3,5-三嗪类,例如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/十三烷基氧基-2-羟基丙氧基)-2-羟苯基]-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-羟苯基)-4-(4-甲氧苯基)-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、2,4-双(4-[2-乙基己氧基]-2-羟苯基)-6-(4-甲氧苯基)-1,3,5-三嗪。
3.金属钝化剂,例如N,N′-二苯基草酰胺、N-水杨醛-N′-水杨酰肼、N,N′-双(水杨酰)肼、N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼、3-水杨酰氨基-1,2,4-三唑、双(亚苄基)草酰二肼、草酰替苯胺、间苯二甲酰二肼、癸二酰二苯基酰肼、N,N′-双乙酰己二酰二肼、N,N′-双(水杨酰)草酰二肼、N,N′-双(水杨酰)硫基丙酰二肼。
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、三(壬基苯基)亚磷酸酯、三(十二烷基)亚磷酸酯、三(十八烷基)亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、二异癸基季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,4-二-枯基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、二异癸基氧基季戊四醇二亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三(叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂基山梨糖醇三亚磷酸酯、四(2,4-二叔丁基苯基)4,4′-亚联苯基二膦酸酯、6-异辛基氧基-2,4,8,10-四叔丁基-12H-二苯[d,g]-1,3,2-二氧杂磷杂环辛烯、双(2,4-二叔丁基-6-甲基苯基)甲基亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯[d,g]-1,3,2-二氧杂磷杂环辛烯、2,2′,2″-次氮基[三乙基三(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯]、2-乙基己基(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯、5-丁基-5-乙基-2-(2,4,6-三叔丁基苯氧基)-1,3,2-二氧杂磷杂环丙烷。
以下亚磷酸酯是尤其优选的:
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-双十二烷基羟基胺、N,N-双十四烷基羟基胺、N,N-双十六烷基羟基胺、N,N-双十八烷基羟基胺、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、衍生自氢化牛脂胺的N,N-二烷基羟基胺。
6.硝酮,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-十八基-α-十六烷基硝酮,衍生自N,N-二烷基羟基胺(其衍生自氢化牛脂胺)的硝酮。
7.硫基增效剂,例如硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻基(dimistryl)酯、硫代二丙酸二硬脂酯或二硬脂基二硫化物。
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,二丁基二硫基氨基甲酸锌,二(十八烷基)二硫醚,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,聚乙烯吡咯烷酮,双氰胺,氰脲酸三烯丙酯,脲衍生物,肼衍生物,胺,聚酰胺,聚氨酯,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,蓖麻油酸钠和棕榈酸钾,邻苯二酚(pyrocatecholate)锑或邻苯二酚(pyrocatecholate)锌。
11.成核剂,例如无机物质,如滑石,金属氧化物类如二氧化钛或氧化镁,优选碱土金属的磷酸盐、碳酸盐或硫酸盐;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(“离聚物”)。尤其优选的是1,3:2,4-双(3′,4′-二甲基苄叉基)山梨糖醇,1,3:2,4-二(对甲基二苄叉基)山梨糖醇,和1,3:2,4-二(苄叉基)山梨糖醇。
12.填料和增强剂,例如碳酸钙,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,流变助剂,催化剂,流动调节剂,荧光增白剂,耐焰剂,抗静电剂和发泡剂。
14.苯并呋喃酮类和二氢吲哚酮类,例如公开在US 4,325,863;US 4,338,244;US 5,175,312;US 5,216,052;US 5,252,643;DE-A-4316611;DE-A-4316622;DE-A-4316876;EP-A-0589839,EP-A-0591102;EP-A-1291384中的那些或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,3-(2-乙酰-5-异辛基苯基)-5-异辛基-苯并呋喃-2-酮。
上述添加剂通常的施加量为0.01-2wt%,基于热塑性聚合物的重量。
本发明的进一步的方面是一种通过使用空间位阻仲胺化合物作为加工添加剂在热塑性聚合物的旋转模塑方法中扩大最佳的峰值温度的方法。
因此,所公开的是一种用于在热塑性聚合物的旋转模塑方法中朝着更高的峰值内部空气温度扩大加工范围的方法。
所述方法包括将空间位阻仲胺合并到热塑性聚合物中并且使聚合物进行旋转模塑方法。
本发明的又一个实施方案是一种用于生产热塑性空心制品的方法,所述方法包括
混合热塑性聚合物与空间位阻仲胺,和
使这种混合物进行旋转模塑方法,其中峰值内部温度范围为约215-约250C,
其中当热塑性聚合物是聚乙烯时,位阻胺不是N,N′-双-(2,2,6,6-四甲基-4-哌啶基)己二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的线性或环状缩合物。
以上给出的定义和优选方案还适用于本发明的其它方面。
以下实施例举例说明本发明。
实施例1:通过旋转模塑方法制备聚烯烃空心制品
100份与己烯共聚的中密度聚乙烯(标称熔体指数3.3g/10min,密度0.938g/cm3)与0.050份的硬脂酸锌以及表1中给出的另外的稳定剂的组合物干混。在190℃在Superior/MPM挤出机中使用24∶1 L/D的螺杆以及Maddock混和头在100rpm将混合物熔融混配成粒料。混配粒料被研磨至均匀粒度(150-500μm),然后进行旋转模塑方法。这种研磨步骤增加了颗粒的表面面积,导致更快的热吸收,因此降低了总能量消耗。旋转模塑方法在实验室规模设备FSP M20″Clamshell″中进行。将被研磨的树脂置于铝模具中,在燃气烘箱中使其双轴旋转。热空气通过鼓风机在所述腔室中循环,同时温度被增加到274℃。保持这一温度达特定的时间,这将得到某一峰值内部空气温度(PIAT),如表2中给出的。随后,打开烘箱并且同时仍然旋转,使用强制空气循环将模具冷却7.3分钟,随后喷水雾1.5分钟,空气冷却2分钟,喷水2.9分钟和空气冷却4.4分钟。在全部加热和冷却循环中,主轴的速度被维持在6rpm,其中旋转比为4∶1。在冷却循环后,打开模具并且取出空心物体。
加工范围被定义为这样的峰值内部空气温度范围(PIAT),其中可以生产出具有高冲击强度的部件。冲击强度是在-40℃根据ASTM D-3763使用Dynatup落锤方法(25lb/20″″)测量的。
表1
表2:结果
01 | 02 | 03 | 04对比例 | 05对比例 | 06 | |
加工范围PIAT的上限[℃] | 227 | 229 | 229 | 216 | 219 | 238 |
在-40℃总冲击能量 | 44 | 45 | 47 | 46 | 50 | 43 |
空间位阻胺 | 仲 | 仲 | 仲 | 叔 | 叔 | 仲 |
数据清楚地表明在不牺牲冲击强度的情况下通过使用空间位阻仲胺化合物有用的加工范围可以显著地朝更高温度移动。
实施例2:通过旋转模塑方法制备聚烯烃空心制品
使用如表3中所述的其它添加剂重复实施例1中给出的程序。结果列于表4。
表3
表4
0378 | 00 | 07 | 08 |
加工范围PIAT的上限[℃] | 198 | 210 | 221 |
在-40℃总冲击能量[J] | 45 | 42 | 42 |
HALS | 无 | 叔 | 仲/叔 |
然而在没有空间位阻胺存在时,如通过峰值内部空气温度测量的加工温度(PIAT)不应该超过198℃,但当空间位阻叔胺存在时,210°是可接受的。然而,这一温度可以被进一步扩展到至多221℃,当根据本发明添加空间位阻仲胺时。
Irganox 3114是酚类抗氧化剂,获自Ciba Specialty Chemicals,
Cyasorb UV 3346是空间位阻仲胺,获自Cytech Industries,
Claims (5)
3.根据权利要求1的用途,其中空间位阻胺化合物的添加量为0.01至5wt%,基于热塑性聚合物的重量。
4.根据权利要求1的用途,其中在旋转模塑方法中,存在着另外的稳定剂,其选自UV-吸收剂、不同于通式(I)或者(II)的空间位阻胺、酚类抗氧化剂、亚磷酸酯或者亚膦酸酯和苯并呋喃酮或者二氢吲哚酮。
5.一种用于在聚乙烯的旋转模塑方法中朝着更高的峰值内部空气温度扩大加工范围至220℃至250℃的方法,
所述方法包括将权利要求1中限定的空间位阻仲胺合并到聚乙烯中并且使聚乙烯进行旋转模塑方法。
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US11267951B2 (en) * | 2010-12-13 | 2022-03-08 | Cytec Technology Corp. | Stabilizer compositions containing substituted chroman compounds and methods of use |
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