TW321658B - - Google Patents

Description

A6 321658 _B6 _ V. Description of the invention (/) (Please read the precautions on the back before writing this page) The present invention relates to a method for preparing olefin polymers, which pseudo-add hydrotalcite, zeolite or metal during the polymerization reaction Gasification and selective stabilizers. The invention is also broader than the olefin polymers obtained. The low-pressure polymerization of olefins and organic gold complex catalysts (such as Ziegler-Natta catalysts) generally results in fine powdered polymers, which go through the extrusion process of the extruder before processing. In this granulation process, substances such as stabilizers, corrosion inhibitors, color enhancers, preservatives or other processing aids are used. However, the granulation process may not be favored or may meet the requirements when encountering high molecular polymers. At present, by using solid supported catalysts to prepare spheres, the polymer in particle form has proved to no longer need to be granulated by extrusion, but can be directly processed. Carriers suitable for the use of these solid catalysts have been discovered, especially spherical magnesium halide with specific particle size, as shown in DE_A — 264 1 9 60. The anhydrous magnesium halide forms an insoluble complex with T i C 14 and the electron supplier, which is then activated by the aluminum alkylene group. Three-dimensional anisotropy and activity will be enhanced when using electron donors such as carboxylic acid esters or compounds containing Si_O-C bonds, as shown in EP-A-45977. The Ministry of Economic Affairs, the Ministry of Economic Affairs and Development, the Employee Consumer Cooperative of the Ministry of Economic Affairs printed and burned because the polymer so obtained no longer needs to go through the granulation process, and then want to add modifiers that are important for long-term stability during processing and polymerization. The addition of many traditional modifiers (such as stabilizers) can interfere with the polymerization of olefins and cause discoloration of the polymer. Further processing machines for polymers such as calanders will be corroded. The corrosion effect of the polymer on the metal surface is generally attributed to the catalyst residue of 82.6. 40,000 This paper was once again used in the SS home standard (CNS) A 4 standard ironing (210 X 297) A6 B6 V. Invention description (7 ) (Please read the precautions on the back before filling in this page). Until now, a corrosion inhibitor had to be added at one stage of processing. It is known that (EP-A-192987 or EP-A-035 0444) polyalkylpiperidine-type steric hindrance amine stabilizers do not interfere with the polymerization reaction, nor do they substantially discolor the polymer, and exhibit excellent thermal vaporization Stabilizer. ^ It was further suggested (EP-A-254348) to add organic phosphites or phosphonates as anti-gasification agents. The addition of polyalkylpiperidine-type steric hindrance amine stabilizers and organic phosphites or pyromates during polymerization is also a known technique (EP_A — 0 3 5 1 3 6 0). It is very surprising It has been found that the addition of hydrotalcite, zeolite or metal oxides and selective stabilizers that do not release water under the reaction conditions will not interfere with the polymerization of olefins, and will substantially prevent the corrosion that may occur during the polymerization reaction , Further addition of stabilizer will achieve excellent long-term stability. According to the information published by the WK Industrial and Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs, the present invention relates to a method for preparing an olefin polymer using a transition metal bracelet medium in a polymerization reaction. The hydrotalcite, zeolite or metal oxide compounds are used to carry out the polymer reaction. The polymerization reaction is preferably carried out in the presence of a solid-bearing transition metal catalyst, which has been prepared, and is composed of an aluminum compound containing at least one alkyl group and a Group IV metal compound of the periodic table. -4-82.6. 40,000 copies of this paper are in general use in the SS home base (CNS) A 4 specifications (210 X 297 public goods) 321658 Afi s A6 B6 5. Description of the invention (present) The polymerizable olefins available for this method It is ethylene, α-olefins such as propylene, butene-1-ene, 4-methylpentene-1-ene or 5-methylhex-1-ene, and mixtures of olefins, typically ethylene-propylene or propylene with a small amount of Blends of high ct-olefins. Propylene polymerization and copolymerization will be favored later. The polymerization catalyst is a transition metal catalyst and typically includes active bidentate magnesium and titanium compounds. Catalysts with other Group IV metals (chromium and calcium) of the periodic table are also suitable for use. The active magnesium dihalide means that the strongest reflection line in its X-ray spectrum is wider than the center line of the corresponding active magnesium halide spectrum. Magnesium dichloride or magnesium dibromide is preferably used as magnesium dihalide. The titanium compound preferably contains at least one titanium halide bond, and the preferred one is titanium tetrachloride. The titanium compound can be used with an electron supplier, a typical electron supplier is a carboxylic acid ester, as shown in EP-A-45977. After the magnesium halide reacts with the titanium compound and, where appropriate, with the electron supplier, the excess titanium compound and excess electron supplier are easily washed away by an inert solvent water, the typical solvent is hexane or heptane . Printed by the Beigong Consumer Cooperative Society of the Ministry of Economic Affairs of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) The catalyst prepared in the manner described reacts with an aluminum compound with at least one alkyl group to activate It is preferably used in a solvent of alkane. Examples of suitable aluminum alkyl groups are A1 (C2HS) 3 or AI (C4H9) 3. It is possible to use an electron supplier as a co-activator, usually an organosilicon compound containing at least one Si- 0-C bond, as shown in EP-A-45977. A typical example of this type of silicon compound is phenyl. Three papers are also suitable for use in the national unitary standard (CNS) A 4 brand (210 X 297 public goods) 82.6. 40.000 * Α6 ____ Β6__ V. Description of the invention (ψ) Ethylene Silane, phenyltrimethylsilane, diphenyldimethylaminosilane, methyltriethylsilane, dimethyldiethylsilane or ethyltrimethoxysilane. Further transition gold catalysts typically include a chromium compound (such as alumina or silicon or a mixture thereof) on a solid support. An example of this type of catalyst, also known as Phillips, can be seen in U S — A — 2 8 2 5 7 2 1. The polymerization reaction with these catalysts can be carried out in a liquid phase or a gas phase in a known method. The liquid phase may conveniently be fatty stear hydrocarbons or the liquid monomer itself. Hydrotalcite, zeolite or metal vapor compounds which do not release water under the reaction conditions are added to the polymerization medium at the beginning or end of the polymerization reaction. The listed compounds of hydrotalcite, zeolite, or gold halide are naturally occurring minerals and synthetically prepared compounds. The hydrotalcite compound can be described by the following general formula: M2 + ix * M3 + X * (〇H) 2-(A "-), · mH20 (I) where M2 + is magnesium, calcium, strontium, barium, zinc, Cadmium, lead, tin and / or nickel, M 3 + is aluminum, boron or bismuth. IH »^ 1 nnn I. 1 ^ 1 · I ^ nnnnn-* (Please read the notes on the back before writing this page) The price of Ziliyin η is printed by the ZTE Standard Residence 8 Workers ’Cooperative Cooperative

ο 2 to ο ο for AxmA 5 and 82.6. 40,000 The paper size is applicable to China In-House Standard (CNS) T 4 specifications (210 X 29? public goods) A6 B6 V. Description of invention (() OH-, C1 -, Br, I-, α〇4-, HC03 ·, CH3CCX>-, C6H5CO〇-, C〇32% S〇42% coo-coo-, (CHOHCOO) 22-, (CHOH) 4CH2OHCO〇-. C2H4 (COO) 22-, (CH2COO) 22-, CH3CHOHCO〇-, Si〇32-, SKV *, Fe (CN) 63-, FeiCN ^ 4 • or HP042-. Other hydrotalcites available for the above-mentioned method The following is & I a Mj + Al2 (〇UAn-) 2. (La) where Μ2 + is at least one of the metals of magnesium and zinc, preferably magnesium. An is C 0 3 2 C00 'C00. t2-, Ο Η-and S 2-anions, η is the anion valence, m is a positive number, preferably 0.5 to 5, X and z are positive numbers, X is preferably 2 to 6, z Is less than 2. The preferred hydrotalcite compound is listed as the following general formula I ·· M2VX · Μ3V (OH) 2 · mH20 / n

(D • Printed by the Ministry of Economic Affairs of Japan, Quercus squamata R, and Consumer Cooperatives where M2 + is magnesium or a solid solution representing magnesium and zinc, An_ is C 〇 /, x is 0 to 0.5, m is 0 to 2. Chijia hydrotalcite has the following chemical formula A 1 2 0 3 · 6 M g 0 ♦ C 0 2 M g 4. S A 1 2 (OH) i 3 4MgO * Al2 〇3 ♦ C 0 2 4MgO * Al2 〇 3 ♦ C 0 2 ZnO * 3Mg〇 * Al2 〇3 ZnO * 3Mg〇-Alz 03 It is also possible to use the zeolite M x / n C (A 1 0 2) x (S i 0 2) y) · WH 2 O (X) where n is the charge of the cation M, 1 2 Η 2 Ο C Ο 3 · 3 9 Η 2 〇6 Η 2 〇C Ο ζ * 8 — 9 Η 2 Ο C Ο 2 * 5-6 Η ζ Ο 5 H z 0 nn kT— nn -Γ- -I-I! N---IJ 1 I nn 11 n 1— n,-(Please read the notes on the back before filling in this Page) This paper size and degree are suitable for China® Home Furnishing Standard (CNS) τ 4 specifications (210 X 297 g) 82.6. 40.000 V. Description of the invention (厶) A6 B6 Μ for the first or second main group of the periodic table For elements, y: x is the number of 0.8 to 1.2, and w is the number of 0.5 to 10. The average pore diameter of the better known zeolites printed by the Ministry of Economic Affairs of the Zhanzhanju Jubei Consumer Cooperatives for use in the above method is 3 to 5 Angstroms. 9 includes the N a A type with an average effective pore diameter of 4 Angstroms. This is also known as 4 zeolite. Examples of suitable zeolites are the following compounds: N a 1 ZC (A 1 0 Z) 1 2 (S ί 0 Z) 1 Z] • 1 2 Η 2 C a 4 • 5 C ( A 1 0 2) 1 2 (S • 0 Z) 1 2] ♦ 3 OH K 9 N a 3 C (A 1 0 2) 1 2 (S 0 Z) 1 2] ♦ 2 7 Η Metal vapors are also available In the method of the present invention, it is better to use divalent metal vapors 9 to be better with metal vapors of the second main group or subgroup of the periodic table 9 and then use zinc oxide or oxide to be better 0 novel compounds at 50 V to 8 0 0 t: dried at temperature to remove unbonded or only slightly bonded water 9 It is mentioned that the compound itself is not ten-minute dry * and has been coated There is anhydrous environment. Drying operation can be carried out in vacuum or inert gas. The surface of the substance can be treated with surface-active reagents such as carboxylic acid or straight-chain alcohol with 8 or more carbon atoms. »Stearic acid can be conveniently used. Hydrotalcite that releases water »Zeolites or metal vapors% compounds or similar synthetically prepared compounds-generally added 0 * 0 0 5 to 5 • 0% weight parameter is preferably 0. 0 1 to 1% weight 1 to Gather (you must read the notes on the back and then write this page) ο 2-Seeking-Ordering-The composition is the benchmark. This method preferably uses an additional stabilizer. -8-This paper > < ^ In case of the use of China National Standards (CNS) A 4 specifications (210 X 29 / male double> 82.6. 40,000 3 ^ 1658 A6 B6 V. Description of the invention (7) A particularly preferred embodiment includes the addition of a compound containing at least one 2, 2, 6, 6-tetramethylpiperidinyl group and a molecular weight of more than 500 or the addition of a phosphorus (III) compound. Use this A 2, 2, 6, 6_ tetramethylpiperidine compound and a phosphorus (III) compound are preferred. The steric hindrance amine is known, preferably piperidine, as a light stabilizer, but here Only acts as an anti-gasification agent, that is, the compound transfers thermal oxidation stability to the polymer. These compounds contain one or more groups of formula I

(Please read the precautions on the back before writing this page) 0), it can be an oligomeric or polypolymeric compound. Particularly important stabilizers are the following tetramethyl shodiniums: a) Compounds of formula I I Central Ministry of Economic Affairs, Central Housing and Industrial and Consumer Cooperatives

0

R (H). Where η is the number of 1 to 4, preferably 1 or 2, R1 is argon, hydroxyl gas

Where η is 1 to base, CX -C base, C 7 -C fangyuan base, Ci—Ce base wake-up base, Cs —Cs 82.6. 40,000 This paper size is used in the aa family standard (CNS) A 4 specifications (210 χ 297 public dreams) Printed by Beigong Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs ^ A6 _B6 _ V. Description of invention) Enyl, cyclopropyl or a CH2 CH (OH) — Z group, where Z is hydrogen , Methyl or phenyl, R1 is preferably Ci-C4 alkyl, allyl, benzyl, acetyl or propylene amide, R2 is hydrogen when η is 1, can be interrupted by one or more gas atoms Ci-Ci 8 alkyl, cyanoethyl, benzyl, cyclopropyl, mono-fatty bar, cyclo-fatty bar, aryl fatty bar monovalent group, unsaturated or aromatic carboxylic acid, amino acid or phosphoric acid , Or a monovalent silyl group, preferably a fatty carboxylic acid group of 2 to 18 atoms, an aliphatic carboxylic acid group of 7 to 15 sulfonium atoms, and an alpha of 3 to 5 sulfonic atoms. Saturated carboxylic acid, or aromatic carboxyl group with 7 to 15 carbon atoms, and when η is 2, R2 is C, _Ci2 alkyl, C4 alkenyl, phenylene dimethyl, aliphatic, cycloaliphatic, Aramid The divalent group of the dicarboxylic acid of the bar or aromatic bar, diamino formic acid or phosphoric acid, or the divalent formic acid group, preferably the fatty bar dicarboxylic acid group of 2 to 36 sulfonate, 8 to 14 boats Aromatic aromatic dicarboxylic acid group with 8 atoms, or 8 to 14 phosphorus deer cyclic fatty strips or aromatic diaminocarbamate groups, when η is 3, R2 is a fatty strip, cycloaliphatic or aromatic tricarboxylic acid Acid trivalent group, aromatic strip triamine formic acid trivalent group or containing phosphoric acid group, or trivalent silyl group, when η is 4, R2 is a fatty strip, cycloaliphatic or aromatic strip of tetracarboxylic acid Four debt base. The substituents defined as Ci- 劚 ^ 2alkyl are typically ethyl, n-propyl • n-butyl, secondary-butyl, tertiary-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n--1--yl or n-h diyl. -1 0- (Please read the precautions on the back before writing this page) 丨 Package · Order · This paper size is suitable for China S Jiaku? Standard (CNS) A 4 brand (210 X 297 public goods) 82.6. 40,000 Printed A6 B6 by the Engong Consumer Cooperative of the China Bureau of Standards and Standards, Ministry of Economic Affairs 5. Description of invention (?) Defined as C i-C i 8 alkyl R2 may be the above-mentioned group, and may also be n-h triyl group, n-h tetrayl group, n-h hexal group or n-h octyl group. R1 defined as C3-C8 alkenyl group, R1 is typically 1-propenyl group, Allyl group, methallyl group, 2-butenyl group, 2-pentenyl group, 2-hexyl coal group, 2-octyl group, 4-one-two-level one butyl one 2-butyryl group. R1 defined as C3-C8 alkynyl is preferably propynyl. R1 defined as C7-Ci 2 aralkyl is preferably phenethyl and benzyl. R1, which is defined as a Ci_C8 alkaldehyde group, is typically a formaldehyde group, a propionyl group, and an octyl group. However, acetaldehyde is preferred, and for a C3 to C5 alkenyl group, acryl is preferred. R2, which is defined as a monovalent group of a carboxylic acid, is typically a monovalent group of the following acids: acetic acid, hexanoic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or zhaoyi (3, 5-two one three tertiary monobutyl A 4- · hydroxyphenyl) propionic acid. R2 defined as a divalent group of monocarboxylic acid is typically a divalent group of the following acids: malonic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, sebacic acid, maleic acid, titanic acid, dibutyl Malonic acid, dibenzylmalonic acid, butyl mono (3, 5-di-tertiary monobutyl-4 monohydroxybenzyl) malonic acid or bicycloheptenoic acid. R2 defined as a trivalent group of tricarboxylic acid is typically trimellitic acid or nitrilotriacetic acid group. R2, which is defined as a tetravalent group of tetracarboxylic acid, is typically butane-1, 2, -1 1- This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 public goods) 82.6. 40,000 I ^^ 1 1-DI -I ί n: 1-ί i ^ n I 1 ^ 1 n 1 ^ 1 I rn 1 ^ 1 1 ^ 1 n 11 n (Please read the precautions on page f before writing this page ) A6 B6 V. Description of the invention (β) 3, 4-—The tetravalent group of tetracarboxylic acid or pyromellitic acid. R2, which is defined as a divalent group of diaminocarboxylic acid, is typically hexamethylenediaminocarboxylic acid or 2,4-methylphenylphenylcarbamic acid group. b) Compound of formula (III) (please read the precautions on the back and then write this page)-installed. Central China Bureau of Economic Affairs Employee Consumption Cooperation Du Yin ¾ where η is 1 or 2, R1 is the same as a), R3 is Hydrogen, C! A C 1 2 aryl group> C ζ — C 5 hydroxy aryl group »C 5 — C 7 cyclic aryl group C 7 — C 8 aralkyl * C 2 — C 1 8 alkanoyl 9 C 3 — C 5 alkenyl or benzoyl »and f R 4 is gas when $ η is 1» C 1 —C 1 aryl group> C 3 — C 8 alkenyl% C 5 —C 7 cycloalkyl 9 —Hydroxyl> radon group 9 oxocarbonyl or ureido% C 1 —C 4 alkyl substituted with epoxypropyl group> formula — C Η 2 — C Η (0 Η) a Z group or — C 0 Ν H—Z group »where Z is hydrogen» methyl or phenyl »or when η is 2» R 4 is CZ—C 1 Z subalkyl 9 C 6 —C 1 ζ subaryl * hypophenyl dimethyl基 »—C Η ZO — C Η (0 Η) a C Η 2 group or a C Η 2 — C Η (〇Η) — C Η 2 — 0 — D — 0 — base father where D is C 2 — C 10 times • C 6 — C 1 5 times aryl group 1 C 6 — C 1 2 Cycloalkyl group 9 or when R 3 is not an alkyl amide group »alkenyl group or benzoyl group * R 4 is also a fatty bar t cyclo fat Strips or aromatic strips of dicarboxylic acids or diaminocarboxylic acids -12- Order ·

82.6. 40,000 pieces of paper again used the Chinese National Floating Standard (CNS) Grade A (210 X 297 mm) 21658 A6 B6 Printed by the Ministry of Economic Affairs, Zhongxingbei Bureau W Industrial and Consumer Cooperative ^ V. Description of Invention (//) The divalent group may also be a C0-group, or when R3 and Ruler 4 are 11 at 1, they may be together a fatty strip, a cycloaliphatic strip or an aromatic 1,2, or 1,3-dicarboxylic acid. Price base. It is defined as a Cl-Cl 2 hospital group or a Ci-Cl 8 hospital group substituent as defined in part a). The substituent defined as C 5 -C 7 cycloalkyl is preferably cyclohexyl. R3 which is C7-C8 aralkyl is preferably phenylethyl, or most preferably benzyl. R3 which is C2-CS hydroxyalkyl is preferably 2-hydroxyethyl or 2-hydroxypropyl. R3, which is defined as C2-Ci 8 alkaldehyde, is typically propyl, butyl, octyl, dodecyl, + hexadecyl, and octadecyl, but preferably is acetyl, which is C3_Cs alkenyl R3 is preferably acrolein. O4 is defined as CZ _c8 alkenyl. R4 is typically allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2- Octenyl. R4 substituted with a hydroxy, cyano, alkoxycarbonyl or ureido substituted Ci-C4 alkyl group typically includes 2-hydroxyethyl, 2-hydroxypropyl, 2- radonylethyl, methoxycarbonylmethyl, 2-Ethylcarbonylcarbonylethyl, 2.-aminocarbonylpropyl or 2- (dimethylaminoformaldehyde) ethyl. The substituents defined as C2 to Ci 2 times alkyl are typically ethylene, propylene 2, 2-trimethylpropene, methine, hexamethine, octamethine, decamethine or dodecane base. -1 3------------------------Please read the precautions on the back before spitting (This page is written) This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 2m) 82.6. 40,000 321658 A6 B6 Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Industry and Consumer Cooperatives «V. Description of Invention (l >) The substituent of C6 — Ci 5th aryl group is typically ortho, meta or para phenylene, 1,4-naphthalene or 4, 4, primary and secondary phenyl. D defined as C6-Ci 2 cycloalkylene is preferably cyclohexene. Illustrative examples of such polyalkyl succinimide compounds are the following compounds: N, —bis (2, 2, 6, 6 —tetramethylethridine—4-monoyl) —N. N — —dibutylhexamethylene Diamine N, N '—bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) mono-N, N-dicyclohexyl-2-hydroxypropene-1,3-diamine

c) Compound of formula (IV) -14- This paper scale is applicable to China National Private Law (CNS) Jia 4 said (210 X 297 public goods) 82.6. 40,000 (please read the precautions on the back before filling this page)丨 Installation_ Order. A6 B6 V. Description of Invention (I Seven)

Where η is 1 or 2 »R 1 is defined as 2 — C 8 alkyl or C 2 — C acetylene secondary base 9 when η is 2 C Η ZO —) 2 base 〇 is defined as CZ — C 8 secondary R 5 may be ethylene 9 1 — methyl ethyl — ethyl — 2 — hydroxymethacrylic acid is defined as C 4 — C Z 2 m yl 2 monoethyl acetyl methacrylic acid d) formula VA > VB and VC (IV), such as a) R5 when η is 1 is C 8 Xiangji secondary group or C4-C2 2, Rs is (-CH2) 2C (group or C2-C8 hydroxyalkylene olefin, propylene, R5 of 2-ethylpropene or 2-oxoalkylene may be a 2-ethyl compound (please read the precautions on the back before filling in this page)-Pack-Order.

IK 15- 82.6. 40,000 is printed on the paper standard of China National Standards (CNS) A 4 now branded (210 X 297 mm) 321658 A6 B6 V. Invention description (/ +)

R (VA)

R

C base alkene 5 C

5 C alkyl alkane 9 C

Alkane Ring 7 C

Alkyl} yl 2 oxy Η alkane C / V 6 C I-formula 2 1 C or, propyl propane oxy cyclic hydroxy, 4-yl C aryl-ο 2 1 c C

6 C

ο ο CIP (Please read the precautions on the back before writing this page) Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-for the type Q- or, 2 base 2 c Q or cc 1 7 1 for R6 p, In C, its 2,, is the base group ηolefin Q in the sub- or ο, C group-benzene-ο or 4 1 group C Ρ ethane:} 4 group 2 C alkane Η I times C 1 2

C 2

Η Η, c C group--alkane, secondary group Η 〇 aryl c 1 time-c 2 ο -1 I 2 c DC Η) c Η 1 ο / i- 2 c I 6 c-is ο D 1 in 2 Its Η, C group,--group. — ^ 2 Aromatic ΗΗ 次 ◦ C 5

C

C 2 The size of clothing paper is in accordance with China National Standard (CNS) Grade 4 (210 X 297 public goods) 82.6. 40,000 KK Central Standards Bureau KK Industrial and Consumer Cooperation Du Yin «A6 ___ [_ B6__ V. Description of invention (β) Cycloalkyl, or a CH2 CH (OZz) CHz — (〇C Hz — CH (OZ #) CH2) 2 — group, where Z; is hydrogen, Ci -Ci 8 alkyl, allyl, benzyl , C2 — Ci 2 alkyl acetyl or benzoyl, T! And D 2 are independent from each other as hydrogen or C 6-C. The aryl group may be a C7-C9 aralkyl group which may be substituted by halogen or Ci (: 4 alkyl group, or Τι and τ2 together form a cs_C 1 2 ring aryl ring with the connected sulfo atom. Defined as C1 — 2 The substituent of the alkyl group is typically methyl, ethyl, n-propyl, n-butyl, secondary-butyl, tertiary-butyl, n-hexyl, n-octyl, 2-ethylhexyl, N-nonyl, n-decyl, n-undecyl or n-dodecyl. The substituents defined as C, -Ci 8 alkyl may be the above-mentioned groups, or may additionally be n-tridecyl, n-one Fourteen radicals, n-hexadecyl or n-octadecyl. The substituents defined as c2_cs alkoxyalkyl are typically methylaminomethyl, ethylaminomethyl. Propylaminomethyl, tertiary -Butylmethyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tertiary-butoxyethyl, isopropylaminoethyl or propylene Gas-based propyl. R7 defined as C3-C5 alkenyl can be 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl. R 7, Ti and C7 are defined as — T2 of C9 aralkyl is preferably phenylethyl, or most It is a benzyl group. The cycloalkane ring formed by Ti and butyl 2 together with the attached sulfo atom can be cyclopentane, cyclohexane, cyclooctane or cyclododecane-17- (please read the notes on the back before writing This page) is installed. Ordered • • 11, This paper scale is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 public)> 82.6. 40,000 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs «A6 B6 V. Description of the invention (4)

ZS Geotechnical 〇 Defined as C2-C4 hydroxyalkyl R7 may be 2-hydroxyethyl, 2-hydroxypropyl 2-hydroxybutyl or 4-hydroxybutyl. R7, Ti and are defined as Cs _Ci. The T2 of the aryl group is preferably a phenyl group, α- or / 9-naythyl group, which may be substituted with halogen or Ci-C4 alkyl group. It is defined as C2-Ci 2 alkyl group is typically ethyl, propyl, 2, 2 -Dimethylpropene, methine, hexamethine, octamethine, eleventh methyl or twelve methine. R7 defined as C4-Ct 2-alkenyl is preferably 2-butene, 2-pentene or 3-hexene. R7, which is defined as C6-C ^ secondary aryl, is typically ortho, meta or para phenylene, 1, 4 primary naphthyl or 4, 4-primary and secondary phenyl. Z — is c2 — Ci 2 alkyl acetyl group may be propyl acetyl group, butyl acetyl group, octyl yl group, dodecyl yl group, but acetyl group is preferred. It is C2-Ci. Secondary hospital base, Ce — Ci 5 times aryl group or Ce — Ci 2 ring secondary hospital group D, as defined in b). Illustrative examples of this type of polyalkylspermidine are the following compounds: 2, 2, 4, 4-tetramethyl-7-oxa 3, 20-diaza-21-gas-bi-spiro [5. 1. 2 〕 One twenty-one ethane 8 Ethyl -3- dodecyl one 1, 3, 8-triaza one 7, 7, 9, 9 one tetramethyl spiro [4. 5] decane one 2, 4 —Diketones or compounds of the following formula: -18- This paper is again universally applicable to China National Standard (CNS) A · 1 specifications (210 X 297 g: ¢) 82.6. 40,000 I nn I n 1 ^ 1 I n- -1 XI-I) I-I-I! ^ N 1 I— n (Please read the precautions on the back before writing this page) A6 B6

NH-C = 0

CH, CH,

CH3 CH,

(Please read the note Ϋ on the back before writing this page) CH, CH :,

NH— C = 0

CH,

ch3 ch3 C — NH / ~ X |) < NH N — C II 〇 ch3 ch3 | loaded · e) Formula V I compound

10 • R (VI), set. Printed by the Employees Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economy ¾

Where n is 1 or 2, R8 is the following formula CH〇CH3 -E- (A) The paper standard is universal Chinese National Standard (CNS). A 4 specifications (21〇X 297 mm) 82.6. 40,000 V. Invention Description (丨) A6 B6 where R1 is defined as a), E is a 0 — or a NR1 1 —, A is C2 — Ce secondary hospital or — (CHz) 3 — 0 —, X is 0 or 1, R9 Defined as R8 or -NR1 1 R12, — OR1 ^, -NHCHz OR1] or -N (C Η 2 Ο R 1 3) 2, R1 ° is defined as R8 or rs when η is 1, where ^ is 2 , Is an Ε—Β—Ε— group, where Β is a C2_Ce subalkyl group that can be interrupted by an N (R1 1) —R1 1 SC! -Ci 2 alkyl group, cyclohexyl, benzyl, or Cl— C4 hydroxyalkyl or the following formula

(Please read the precautions on the back before writing this page) -Install ------. 玎 | Printed by Beigong Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs ¾ R12gC1-Cl2 alkyl, cyclohexyl, benzyl, C 〗 -C4 hydroxyalkyl and R1 3 are hydrogen, Ct-Ct 2 alkyl or phenyl, or R1 1 and R1 2 when taken together is (: 4-C5 alkyl or 〇4-C5 oxane Base, typically or one type base -ch2ch2 -ch2ch2 N —R1 -2 0-* CH2CH2 The paper size is applicable to China National Standards (CNS) A 4 specifications (210 X 297 mm) 82.6. '40, 000 A6 B6 V. Invention Description (if)

Or R and R 1 2 are individually the following formula 3 Η C Η

NH-A-

H (please read "Notes on the back and then fill in this page"). The Central Committee of Bureau of Economic Affairs, Employee and Consumer Cooperative of the People's Consumer Cooperative, is defined as C, _Ci 2 alkyl. The substituents are typically methyl, ethyl, n-propyl, n Monobutyl, secondary monobutyl, tertiary monobutyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-twelve base. The substituent defined as Ct_C4 hydroxyalkyl is typically 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl. A defined as C 2 -C 6 alkyl can be ethylene, propylene, 2,2-dimethylpropene, tetramethine or hexamethine. -2 1-This paper again uses the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 82.6. 40,000 A6 B6 V. Description of the invention (/) R1 1 and R1 2-starting from c4 -CS Hypoalkyl or oxalinyl can be methine, pentamethine or 3-oxapentane. Examples of such polyalkylpiperidine compounds are the following compounds: (Please read the precautions on the back before filling in this page) -Package ·

R R, N 'R -NH-CH2CH2CH2-0

Order. Printed by the R-Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economics «

ch2-ch2-nh-

-twenty two-

82. (3. 40,000 paper standards are applicable to China National Standards (CNS) f 4 Sao Ke (210 X 297 public goods) 321658 A6B6 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 52

(Please read the precautions on the back before writing this page) Binding · Ordering · This paper scale is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 82.6. 40,000 V. Description of invention R.

6 6 A B 75) R =) 3-n h2) c Nά h2) (c R ± 3-n h2) r—n- (c

CIN

(Please read the note Ϋ on the back before filling in this page)-installed. 76) h2) (c I R— · Ν) 3 · H (ci -N R · R- R i% h2) c

R

H3 H3 H3

tYA 5> NC4H order. Printed by R Industry and Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs «77) CH〇 CH3 \ J x CH3 ^^ 'N ^^' CH3 ch3 3

ch3 rr ch3 IIII RN — (CH2) 3— N — (CH2) 2— N — (CH2) 3—N ——R -24 · This paper is again applicable to China National Standard (CNS) A4 (210 X 297 mm) 82.6. 40,000 A6 B6 5. Description of the invention (8) R =

CH3 (Please read the notes on the back before writing this page) 78) 79)

N-C4H9 -n n «^ 1 1— · 1 If In m ^ 1- l ^ i n? Printed by the Ministry of Economic Affairs, Central Standard, WC Industrial Consumer Cooperative

NIC

N

CH3 ch3 H9

N— (N-CH2CH2-OH c4h9 ch3 ch3 t-sheet scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) 82.6. 40,000 A6 B6 V. Description of invention (Mf)

(Please read the precautions on the back before writing this page) — Binding. Order. Printed by the R & C Consumer Cooperative Society of the China Bureau of Standards and Economics of the Ministry of Economic Affairs «-26- Specifications (210 X 297 public dreams) 82,6 · 40,000 V. Description of the invention (β) A6 B6 < Please read the precautions on the back before writing this page) A better or better than 0, a base containing pyridine bit # single The base is covered with a quaternary structure | Jun 6 its, > 6 compounds, combined with 2 compounds, combined with 2 poly} or I combined (poly-oligomeric) with f ethers and poly, amine, azide triacid Polyalkylene is amine-propylate. It is a compound of 2 types. Here is an example of poly}, carbamide poly <, polyester · acid-methanyl silamine poly. Polyesters, esters, amino acids, polyolefins, propionated amines, aldehydes, and aldehydes. This polymethyl group contains the stated agent. Guang ο ο ο pipe 2 kiolane to the 4 2 I is 6 m, 6 in its order. The paper printed by the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Consumers Cooperative Society of the People's Republic of China again used the Chinese national standard rate (CNS) A 4 Specifications (210 X 297 public dreams) 82.6. 40,000 321658 a6 B6 5. Description of the invention (4

0II 81)

C-CH2-CH2 ~ C-O-CH

Ο- m (please read the notes on the back before filling this page) 82) CH3 ch3

ch3 ch3

ΟII

ΟII — ~ P: H2-CH2-N V—O one C- {CH2) 4— C-Ο ch3 ch3

o 〇11 U N-CH5-CH2-〇- C- (CH2) 4- c · X m-installed · CH3 ch3 ordered · Printed by Beigong Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs 28 This paper size is suitable for 3 samples in China Standard (CNS) Grade A 4 (210 X 297 Gonglian) 82.6. 40,000 V. Description of the invention (β 83)

ch3 I 3 NH-C — CH〇— C-CH〇 I I 3 ch3 ch3 84)

(CH2) 6- A6 B6 ch3,, c2h5

NH— ^-(CHgJrNH- c2h5

• N

CH2-CH (OH) -CHr 85) .N ‘

86) Printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Development of the Ministry of Economic Affairs

C4H9 • C — c4h9 29- m -1 m 〇 II • c

Each paper scale applies the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 82.6. 40,000 321658 A6B6 5. Description of the invention (7 /) 87) CH3CH3

(Please read the notes on the back before filling out this page) 8) 8

H2 c c

on-c h2) (c To = -c

E 89) 90)

OHC H5 2 cIc -a 0 = 0 c c

o m H3 Printed by Zhonggong Standards Bureau, Ministry of Economic Affairs

This paper scale is applicable to the Chinese National Standard (CNS) Grade 4 (210 X 297 public goods) 82.6. 40,000 V. Description of the invention (^) CHIC- \ J / 91 c 3-n 1 oc6h

o A6B6 (Please read the notes on the back before writing this page) 92) 93)

丨 Installed. Ordered. Printed by the R-Consumer Cooperative of the Bureau of Loss of Standards of the Ministry of Economics 94)

6

mr JOMnc H2 · This paper scale is applicable to the S National Capture Standard (CNS) A 4 specifications (210 X 297 public greed) 82.6. 40,000 V. Description of the invention (and 95)? H3 — Si — 0 — (〇η2), ο m A6 B6

CH3 (Please read the notes on the back before filling this page) H9C4 (R) N N N (R) C4H9 Y, Νγ

— NH (CH2) 3 丨 loaded. 96)

H9C4 (R) N

N

'' 'jl— N — (CH2) 2— N ΝγΝ N (R) C4H9

(CH2) 3 NH _R · 2 · 3 N ^ N h9c4 (r) n ^ n ^ N (R) C4H9. Red R ’printed by the Industrial and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs:

H9C4 (R) N, NN (R) C4H9 This paper is again applicable to the Chinese National Floating Standard (CNS> A4 present grid (210 X 297 mm) 82.6. 40,000 A6 B6 V. Invention description (々 () Among the photo-safety agents, categories e) and f) are suitable, especially tetraalkyl piperidine containing secondary-triazinyl groups, and other suitable compounds are compounds 74, 76, 84, 87, 92 and 95. The amount of tetramethylpiperidine added depends on the desired degree of stability, generally from 0.01 to 5% by weight, preferably from 0.05 to 1% by weight, based on the polymer. Preferably, the molar ratio of tetramethylpiperidine and aluminum alkyl is not more than 1. The phosphorus (I I I) compound added to the polymerization reaction as a selective stabilizer may be a phosphite, a sulfonate or a sulfite. It may contain one or more high-value phosphate groups. It is better to use the phosphorus (I I I) compound of formula A, B, C or D (please read the precautions on the back before writing this page) • Pack. Order · p-or3

Ri R ^ O — P — R4— P OR3 r2

A

B R1 0-V. / -0: DO-r7o

Ri P-Rg R80 Printed by the Ministry of Economic Affairs

C

D 33- 82.6. 40,000 The size of this paper is applicable to the Chinese Garden Standard (CNS) A4 specification (210 X 297 public dreams). «A6 B6 V. Invention description (point) Among them, Ri and Rz are independently another Ci-Ci 2 alkyl. C £ _Cs cycloalkyl, phenyl, phenyl substituted with one to three Ci-Ci 2 alkyl, or an OR3 group. R3 is C6-Cz. Alkyl group, Cs-Ce cycloalkyl group, phenyl group or phenyl group substituted with one to three-valued Cl-Cl 2 groups, and R4 is unsubstituted phenylene or phenanthrene or Ci-C: 2 A phenylene group or a nylenyl group substituted by a phenyl group, or a -10 Rs — 0 — group, wherein Rs is an unsubstituted phenylene group or a nylenyl group or a phenylene group substituted by -C! Or Phenyl, or a P.hen — only 6 — Ph en —, where Phen is a phenylene group, and Re is a ◦ 一 • 一 S —, -S 0 2-,-CH2-or -C (C Η 3) 2-, R7 and R8 are independently another phenyl group or a phenyl group substituted with one to three ® Ci —Ci 2 alkyl groups, the two R7 and R8 substituents can be substituted by C i -Ci twice The alkyl group is linked to R9 as fluorine, atmosphere, bromine or iodine, preferably fluorine. Among the compounds of formula A, it is preferred to use Ri and Ruler 2 as 0R 3 and R3 as C6-C2. Alkyl, phenyl or phenyl substituted with one to three values Ci-Ci 2 alkyl. Among the compounds of formula B, compounds in which R2 is -〇R3 and R3 is phenyl or phenyl substituted with one to three-value Ci-Ci2 alkyl are preferably used, and R4 is secondary phenyl. -34- (Please read the precautions on the back before writing this page)-Pack. Order. This paper is suitable for use in S3 Jiake Zhun (CNS) A 4 gauge branding (210 X 297 mm) 82.6 . 40,000 V. Description of the invention (θ) (please read the note on the back side of the intercalation item first and then write this page). Among the compounds of formula C, it is better to use the ruler 1 as 10r3 and R3 as phenyl Three Cl _Cl 2 alkyl substituted phenyl compounds. Preferably, a phosphorus (I I J) compound containing at least one P-◦Ar group is used, wherein Ar is a monoalkylphenyl, dialkylphenyl, or trialkylphenyl group. Examples of usable phosphorus (III) compounds are: triphenyl phosphite, decyl diphenyl phosphite, phenyl didecyl phosphite, ginseng (nonylphenyl) phosphite, tris (lauryl) ) Phosphorous acid salt, tris (octadecyl) phosphite, distearyl erythritol pentaerythritol diphosphite, ginseng (2, 4-two one three tertiary monobutylphenyl) phosphite, diisodecyl Pentaerythritol diphosphite, bis (2,4-dione-tertiary monobutylphenyl) pentaerythritol diphosphite, ginstearic aldehyde sorbitan ginseng phosphite, tetrabis (2,4-dione Tertiary monobutylphenyl) _4, -diphenylphenylphosphinic acid. Salt, bis (2, .6-di-tertiary-butyl-4 monomethylphenyl) pentaerythritol diphosphite. The amount of the phosphorus (III) compound depends on the amount of the piperidine compound added, and the general amount added is 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, based on the polymer. Printed by the quasi-Mabei Consumer Cooperative in the Ministry of Economic Affairs In addition to phosphorus (III) compounds, co-stabilizers and modifiers that do not interfere with the polymerization reaction may be added. It is preferable to add a steric hindered phenol type antioxidant to the polymerization reaction. These phenols are standard anti-gasification agents for organic matter and are often used in stabilizers. The description of this type of phenolic strip anti-gasification agent is * 35- 82.6. 40,000 This paper is again suitable for the Θ® home frame standard (CNS) A 4 specifications (210 X 2 & 7 mm) Α6 Β6 321658 V. Invention Description (Can) Examples are: 1. Hospital-based single age, such as 2, 6-di-one-butyl-4-methylphenol, 2--tert-butyl- 4,6-dimethylphenol, 2, 6 — Tert-butyl-4-ethylphenol, 2, 6 — Di-tert-butyl-4 4-n-monobutylphenol, 2. 6 — Ditert-butyl-1 4-isobutyl Phenol, 2, 6-di-cyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4, 6-dimethyl age, 2, 6-twenty-one eighty-one base 4 —Methylbenzene, 2,4, 6 —Trisylcyclohexylhydrazine, 2, 6 —Di-tert-butyl-4 methoxymethylphenol, 2, 6 —Dinonyl-4-methyl Phenol, 2, 4-dimethyl-6- (1, monomethyl-undecane-1, monoyl) phenol, 2,4-dimethyl-6- (1 'monomethyl-decane One 1 'one base) hearth, 2, 4- -dimethyl one 6-(1' one methyl one thirteen-one 1 'one base) phenol and mixtures thereof. 2. Alkylthiomethylphenol, such as 2,4-di-octyl-thiomethyl-6-to-butylphenol, 2,4-dioctylthiomethyl-6-methyl Hearty, 2,4-di-octylthiomethyl-6-ethyl-song, 2,6-di-dodecylthiomethyl-4-nonylphenol. 3. Hydroquinone and alkylated hydroquinone, for example, 2, 6-di-one-butyl-4-methylaminophenol, 2, 5-dione-to-one-butyl monohydroquinone, 2, 5--2 One special-pentyl-M-Kun, 6-diphenyl-4, 18-Yuanyuan base gas age, 2, 6_ two-holding one butyl monohydroquinone, 2, 5-two-one waiting one butyl-3 6-This paper scale is applicable to China National Standard (CNS) Grade 4 (210 X 297 public goods) (please read the precautions on the back before filling out this page) Printed by the cooperative 82.6. 40,000 Printed and burned A6 B6_ by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (β) bis 4-hydroxyanisole, 3, 5-di-tert-butyl-4 monohydroxybenzo Ether, 3, 5-di-tert-butyl-4-hydroxyphenylstearic acid, and bis (3,5-dione-wait-butyl-4-hydroxyphenyl) adipate. 4. Hydroxylated thiodiphenyl ether, for example, 2, 2 * monothiobis (6-tert-butyl-4-methyl disc), 2, 2-thiothiobis (4-octylphenol) , 4,4 'monothio-bis (6-tert-butyl-3-methylphenol), 4,4' monothio-bis (6-to-butyl-2-methylphenol), 4 , 4 'monothio-bis (3,6-dione-two-level pentylphenol) and 4, 4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide. 5. Alkylidene-bisphenol, for example, 2, 2-methine-bis (6-tertiary monobutyl-4-methylphenol), 2, 2 'once-methyl-bis (6-tertiary— Butyl-4-ethylphenol), 2, 3 'once methyl-bis [4-methyl-6- (cc-methylcyclohexyl) phenol], 2,2' once methyl-bis (4-one Methyl-6-cyclohexylphenol), 2, 2 * -methine-bis (6-nonyl-4-methylphenol), 2, 2 'once methyl-bis (4,6-dione One butyl phenol), 2, 'one ethyl fork one pair (4, 6-two one three tertiary monobutylphenol), 2, 2' one ethyl fork one pair (6 three tertiary one butyl one 4 (Isobutylphenol), 2, 2 'once methyl-bis [6-(α-methylbenzyl) _4 nonylphenol], 2, 2' once methyl-bis [6 — (α, α — Dimethylbenzyl) -4 4-nonylphenol], 4 -37- This paper standard universal tag home kneading standard (CNS) methyl methine (210 X 297 public if) 82.6. 40,000 .I — III IIILIIIIIIIIIIIII I .IIIII '11 (Please read the notes on the back, s and then fill out this page) Employee Consumption Social Printing 5 < A6 B6 V. Description of the invention (private), 4 ′ once methyl one pair (2, 6 — tertiary monobutylphenol), 4, 4 ′ once methyl one pair (6 — tertiary monobutyl Group 2-methylphenol), 1, 1-bis (5-tertiary monobutyl-4 4-hydroxy-2-methylphenyl) butane, 2, 6-bis (3-tertiary monobutyl) -5 -methyl-2-hydroxybenzyl) -4 methylphenol, 1, 1, 3,-ginseng (5-tertiary _butyl-4-Xiangyl-2-methyl) butan, 1 , 1-bis (5-tertiary-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl hydrogenthiobutane, ethylene glycol bis [3, 3-bis ( 3 'one-wait-butyl-4'-alkylphenyl) crotonate], bis (3-tertiary monobutyl-4 4-hydroxyl 5-methylphenyl) dicyclopentadiene, bis [2-(3 'one tertiary one butyl one 2' one hydroxy one 5 'one methyl benzyl) 6-to be a butyl φ group a 4-methylphenyl] terephthalate, 1, 1 A bis (3, 5 dimethyl-2-hydroxyphenyl) butane, 2, 2-bis (3, 5 — bis-one-butyl-4-hydroxyphenyl) Alkane, 2, 2-bis (5-tertiary-butyl-4-hydroxy-2-methylphenyl) _ 4-n-dodecyl hydrogen thiobutane and 1,1, 5, 5-four (5-tertiary 1-butyl-4 4-methyl-2-methylphenyl) penthouse. 6. Ο —, N — and S —benzyl compounds, examples 3, 5, 3 ′, 5′-one-four-three tertiary-butyl_4, 4′-dihydroxydibenzyl ether, octadecyl— 4-Hydroxy-3,5-dimethylbenzyl hydrosulfoacetate, ginseng (3,5-dione-tertiary-butyl-4 4-hydroxybenzyl) amine, bis (4-tertiary monobutyl) 3_Hydroxy-1,6-dimethylbenzyl) dithio-p-benzene-3 8-The standard size of this paper is the Chinese SZYZ (CNS) A4 Clam (Mo X 297 mm) 82.6. 40,000- ---- TII I --------- 'Γ — -------- II Order (please read the precautions on the back before filling in this page) _B6 V. Description of Invention (β) 2 Formate, bis (3,5-dione-tertiary-butyl-4-hydroxybenzyl) sulfide, and isooctyl-3,5-tertiary monobutyl-4 4-hydroxybenzyl hydrothioacetic acid ester. 7. Hydroxybenzylated malonate, such as di-octadecyl, 2,2-bis (3,5-di-tertiary_butyl-2-hydroxyfluorenylbenzyl) malonate, di Octadecyl 2- (3-tertiary-butyl-4-hydroxy-5-methylbenzyl) malonate, behenyl hydrogenthioethyl, 2,2-bis (3 , 5-bis-tertiary monobutyl-4-hydroxybenzyl) malonate, bis [4- (1, 1, 3, 3-tetramethylbutyl) phenyl] 2, 2-bis (3 , 5-di-tertiary monobutyl-4-hydroxybenzyl) malonate. 8. Hydroxyfluorenyl benzyl-aromatic compound, such as 1, 3, 5-ginseng (3, 5-di-tertiary monobutyl-4 4-hydroxybenzyl)-2, 4, 6-trimethylbenzene, 1, 4 a bis (3, 5-bis one tertiary monobutyl a 4-hydroxybenzyl)-2, 3, 5, 6-tetramethylbenzene, 2, 4, 6-ginseng (3, 5- Two one three tertiary one butyl-4-hydroxybenzyl) phenol. Central Bureau of Standards of the Ministry of Economic Affairs β: Industrial and Consumer Cooperatives, India 9. Triazine compounds, for example, 2, 4-bis-octyl hydrogen sulfide-6-(3, 5-two one three level-butyl one 4-Xiangji Anilino) -1, 3,5-triazine, 2-octylhydrothio-1, 4,6-bis (3,5-di-tertiary-4-hydroxyanilino) -1,3,5-tris Azine, 2 — Xin-39- 82.6. 40.000 (please read the precautions on the back before filling in this page) This paper size is applicable to China National Standards (CNS) Grade A 4 (210 X 297 public goods) A6 B6 321658 5 2. Description of the invention (#) Hydroxythio-1, 4, 6-bis (3., 5-di-tert-butyl-1, 4-phenyl phenylamino) 1, 3, 5-triazine, 2, 4 , 6-ginseng (3, 5-bis one tertiary-butyl one 4-hydroxyphenoxy)-1, 2, 3-triazine, 1, 3, 5-ginseng (3, 5-two one ternary 1-Butyl-4-hydroxybenzyl) isoradon urate, 2, 4, 6-ginseng (4-tertiary monobutyl-3-hydroxy-2, 6-di-methylbenzyl) isocyanurate , 2, 4, 6, 6-ginseng (3, 5_ two one three tertiary monobutyl one 4-hydroxyphenyl ethyl)-1, 3, 5-triazine, 1, 3, 5- (3, 5-di-tertiary monobutyl-4-hydroxyphenylpropanyl) hexahydro-1, 3, 5-triazine and 1, 3,5_ ginseng (3, 5-dicyclohexyl mono 4 Monohydroxybenzyl) isoradon urate. 10. Benzyl phosphate, such as dimethyl 2,5-dione-tertiary-butyl-4-hydroxybenzyl phosphate, diethyl 3,5-dione-tertiary 4-hydroxybenzyl phosphate , Dioctadecyl 3, 5-dione-tertiary monobutyl-4-hydroxybenzyl phosphate, dioctadecane, 5-tertiary monobutyl-4-hydroxy-3-methylbenzyl Calcium salt of phosphoric acid ester and monoethyl 3,5-dione-tertiary-4-hydroxybenzyl phosphate. 1 1. Acylaminophenol, for example, 4-hydroxylauric acid aniline, 4-monohydroxystearic aldehyde aniline, and octyl N- (3, 5-dione-tertiary monobutyl-4 4-hydroxybenzene Group) carbamate. -4 0- The size of this paper is common to China S Family Partner Standard (CNS) Grade A (210 X 297 mm) ------- 1 ---.----------- -Install ------ order- '--(please read the precautions on the back before writing this page) Employee Consumer Cooperative of the Chinese Ministry of Economic Affairs Standards Bureau Yin Zi 82.6. 40,000 Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Printed A6 B6 V. Description of the invention (β) 12. β — (3, 5 — Two one three tertiary monobutyl one four monophenyl phenyl) ester of propionic acid and unit or polyol, such as methanol and ethanol , 1,6-Hexanediol, 1,9-nonanediol \ ethylene glycol, 1,1-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, Ginseng (hydroxyethyl) isodonyl urate, Ν, Ν 'bis (hydroxyethyl) oxalate diamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethyl hexanediol, tri Methylpropane and 4-hydroxymethyl-1 phosphorus-1, 2, 7-7-trioxane [2.2.2] octane. 13. β- (5-tertiary monobutyl-4-hydroxyphenyl) propionic acid esters with units or polyols, such as methanol, ethanol, 1,6-hexanediol, 1, 9-nonanediol , Ethylene glycol, 1, propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, ginseng (hydroxyethyl) isocyanurate, Ν, Ν ' A bis (hydroxyethyl) oxalate diamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylpropane and 4-hydroxymethyl-1-phospho-2, 6, 7-Trioxabicyclo [2. 2] octane. 14. Ester of β- (3,5-dicyclohexyl-4-monohydroxyphenyl) propionic acid with units or polyols, such as methanol, ethanol, 1,6-hexanediol, 1,9-nonanediol , Ethylene glycol, 1, -propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, ginseng (hydroxyethyl) isoradon urate, Ν, Ν ' A pair of (hydroxyethyl) oxalic acid di-4 1- The standard of this paper is applicable to China National Standard (CNS) A 4 gauge branding (210 X 297 public goods) 82.6. 40,000 < Please read the notes on the back * fill in This page) _Set · Order-s. A6 ____B6 V. Description of the invention (Miao) Wake amine, 3 ~ thioundecyl alcohol, 3-thiopentadecanol, trimethyl hexanediol, trimethyl propanol and 4 One hydroxymethyl-1, one phosphorus-2, 6, 7-trioxabicyclo [2.2.2] octane. 15. (3, 5-di-tertiary monobutyl-4-hydroxyphenyl) propionic acid esters with units or polyols, such as methanol, ethanol, 1,6-hexanediol, 1,9-nonane Glycol, ethylene glycol, 1, propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, ginseng (methyl ethyl) isocyanurate, N , Ν'-bis (hydroxyethyl acid diamide, 3-thiol-alcohol, 3-sleep pentadecyl alcohol, trimethylhexanediol, trimethylpropane and 4-hydroxymethyl-1 phosphorus-one 2. 6, 7-trioxabicyclo [2. 2. 2] octane. 16. ^-(3, 5-di-tertiary monoyl-4 4-hydroxyphenyl) propionic acid aldol, such as N, Ν, a bis (3, 5-bis one tertiary monobutyl 4-hydroxyphenyl propionaldehyde) hexamethylene diamine, acid aldol, such as Ν, Ν, a bis (3, 5-two one three Grade one butyl four 4-hydroxyphenyl propionaldehyde) trimethylene diamine, acid amine, such as Ν, Ν 'a double (3, 5-two one special one butyl four 4-hydroxy phenyl propionaldehyde)胼. The better antioxidants printed by R Industry and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs are listed on 6, 8, 9, 12, 13, 13, and 16. , Especially 6, 8, 9 and 12, the particularly suitable anti-gasification agent is octadecyl / 3— (3,5 -two-one three-level one butyl one four one hydroxy-42 ′ 82.6. 40,000 ( Please read the precautions on the back before filling in this page> This paper is again applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 public goods) A6 B6 321658 V. Description of the invention) phenyl group) 1 C Acid salt and 1, 3,, 5-ginseng (3, 5-bis-tertiary monobutyl-4 -hydroxybenzyl)-2, 4, 6-trimethylbenzene. The amount of anti-gasification agent added depends on phosphorus (III) Depending on the number of compounds, the general amount added is 0.005 to 0.5% by weight, preferably 0.01 to 0.2% by weight, based on the polymer. The present invention will be in the following The non-limiting examples are described in more detail, in which the parts and percentages in the description and patent application range are expressed by weight unless otherwise stated. Example 1: Preparation of catalyst 25 g of anhydrous gasification Magnesium and 5 grams of tetra-aluminated titanium-ethyl benzoate complex are ground in a ball mill with stainless steel balls at room temperature (about 221C) and argon for 24 hours. The solid contact thus prepared The medium composition contains 2% titanium. Propylene polymerization The polymerization reaction is carried out in a 3-liter stirring and thermostatically controlled stainless pin autoclave. The autoclave is evacuated at 1 IOC (13Pa) for 30 minutes before the start of the polymerization reaction. Afterwards, it was flushed with propylene gas at 110 ° for 30 minutes. The autoclave was cooled to 2〇, 300 mg of S-1, 300 mg of H-1 and 300 mg of P-1 were added to the autoclave as a solid, Or form a 5-10% solution in hexane. Then 25 mg of the solid catalyst component was half active with 4 mmol of triethylaluminum and 1.6 mmol of triethylaminophenyl silane in 25 ml of hexane for 10 minutes, suspended in argon In the autoclave, the autoclave was washed with half of the solution. This standard is in the general standard ga Jiake quasi (CNS) A 4 cash (210 X 297 public goods) — ^ 1--1 mn HI n_-i ... .. II— n I * nm 1 ^ 1 I nnnnn (Please read the precautions on the back before writing this page) Printed by the Consumer Cooperative Society of the Ministry of Economic Affairs and Standards Bureau 54 82.6. 40,000 A6 B6 V. Description of invention (4 > ) • After washing, the Like is closed, and hydrogen (6kPa) and 600 grams of liquid propane are burned. With stirring, the autoclave contents were heated to 70 ° C and kept at this temperature for 4 hours. Excess propylene was poured out, and the polymer thus obtained was treated with 10 ml of isopropanol at 701C to deactivate the catalyst. It was then dried under vacuum at 70 * C for 1 hour. The following tests were conducted on the polymer. In the corrosion test, the polymer was molded at 280t: hot press plate for 30 minutes. • The iron plate must be clean. The iron plate is then stored at room temperature (approximately 2 2 υ) at 100% humidity for 24 hours. Visually evaluate the corrosion results. The color of the polymer is shown by the yellowness index (γ I), tested according to ASTM D 1 9 2 5 — 7 0. Comparative Example 2: The degree of Example 1 was repeated, but using 300 mg of S-1, the catalyst yield of the polymer was the same, but it was severely corroded, and the yellowness of the iron plate. The index was 2.5. 5 Examples 3 and 4: · Repeat the degree of Example 1, but use 300 mg of S-2/300 mg of S-5 instead of S-1. Obtained polymer corrosion iron plates are not significant / slightly, the yellowness index of the iron plates are 2. 3/2. 2 Ο Example 5: Polypropylene powder prepared according to Example 3 is used in the 2 3 0 CWBrabender -44 stomach paper size. The Chinese and Western National Standards (CNS) A 4 specifications (210 X 297 mm) (please first Read the precautions on the back and then write the book)-installed. Booked · Printed by the Central Prototype Bureau of the Ministry of Economic Affairs, R Industrial and Consumer Cooperatives ¾ 82.6. 40,000 321658 A6 B6 Printed by the Ministry of Economic Affairs in the Ministry of Economic Affairs, Cooperative and Consumer Cooperatives V. Invention Instructions (Dipper) After being processed for 10 minutes in the plastograph, remove the melted melt from the kneader and press it into a plate of about 5 mm. In the corrosion test, the iron plate did not corrode after the melting process. Comparative Example 6 The polymer prepared according to Example 2 was processed as described in Example 5, and the iron plate was severely corroded after the melt procedure. Examples 7 and 8 The stability of the polymer to oxidation degradation is the time when the polymer undergoes significant embrittlement during the aging process of the high-temperature oven. This test uses the molded polypropylene powder obtained as described in Example 1 at 2 3 Ot: 300 mg of S-1, 300 mg of H-1, 300 mg of P-1 and 300 mg of S-5, 300 mg of H-1 and 300 mg of P-1. The time for the two polymers to embrittle in an oven at 135C is 11 days. Comparative Example Θ: · Polymers were prepared and tested according to Examples 7 and 8, but S-1 and S-5 were not added, and embrittlement occurred after 11 days. This finding means that the addition of S _ 1 and S -5 will not affect the stability of polymer gasification degradation. Comparative Example 10: A polymer was prepared and tested according to Examples 7 and 8, but S-1 and S-5, and H-1 and P-1 were not added, and embrittlement occurred after 1 day. -4 5-This paper scale is applicable to the sa family standard (CNS) A 4 gauge (210 X 297 male dreams) 82.6. 40,000 I β—I 11 nn —4 m I— mnnn it ϋ I il- 1 I- n 1 1 * ^ in-one '. (please read the notes on the back before writing this page) 321658 A6 B6 V. Description of Invention (#) Examples of printing and distribution by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1 1 1 1 4 • The polymerization reaction was carried out as described in Example 1, but using 4 4 mg of solid m medium component% 6 • 4 millimoles of triethylaluminum and 2 • 4 millimoles of triethoxyphenylsilane. The following compounds were used. Substitute for S-1 and Η-1. Example Additive Corrosion Color Index 1 1 Η-1 and S-3 are slightly 2. 3 1 2 Η-1 and S-4 are slightly 2.5 5 1 3 Η-2 and S A little bit 2. 5 1 4 Η — 3 and S — 3 little 2.8 Examples use the following additives 〇S — 1 = c M S 4 • 5 A 1 2 (0 Η) 1 3 • C 〇3 • 3 • 5 Η ZO 0 (This compound is sold by K y 〇Wa Chemical Company (Japanese) $ trade name is D Η Τ-4 A) 〇 This compound is pseudo-vaporized in 9 5 after five vacuum vaporization treatment 〇S-2 c Μ S 4 5 A .1- Z (0 Η) 1 3 • C 〇3 • 3 • 5 Η 2 0] Roasting (This compound is sold by K y 〇W a Chemical Company (Japanese) 9 trade name is D Η Τ-4 C) 0 S-3: zinc oxide (dry) 0 S-4; molecular sieve 4 A (dry) 〇S-5 gasification m (dry) 〇-4 6- (please read the notes on the back first (Fill in this page again) This paper scale is applicable to a 3 sample standards (CNS) A4 specifications (210 X 297 mm) 82.6. 40,000 321658 V. Description of invention A6 B6 Η-1 HNR _ (CH2) 6-NR-

N.

^ jj—NR- (CH2) 6-NR- H NH Itsrt. CgH-jy ΪΑη > 2500 (Please read the precautions on the back before writing this page) 丨 Install. H-2:

R R

I I

R-NH- (CH2) 3-N — (CH2) 2 —N- (CH2) 3-NH-R

R CH3 ch3 N- \ N-CH3

Νκ N

CHo CH3 c4h9-n

CH3, CHg NJ J / Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Industry and Consumer Cooperatives «CH3 CH3 -4 7- This paper scale is applicable to the Chinese National Standard (CNS) Jia 4 (2U) X 297 mm) 82.6. 40,000 321658 A6 B6 5. Description of the invention (Μ) Η-3:

ch3___JL > -ch3 'NH C'H3 ch3 1 ^ > 1500 P-1

C (CH3) 3 ----------, ------- one ------ installed ------ ordered (please read the notes on the back before writing page)

S 4 8 printed by the Central Standards Bureau of the Ministry of Economic Affairs-Cooperative Consumer Cooperative-This paper scale is applicable to China's S Jia Ke Zun (CNS) Grade 4 (210 X 297 mm) 82.6. 40,000

Claims (1)

..Λ * \, 4Η > \ Α8 々 'Β8 M C8 D8 々, patent application scope 1. A method for preparing polypropylene using transitional gold catalyst in polymerization reaction * which includes the addition of at least one of 1 0 0 Up to 40 ◦〇Hydrotalcite, zeolite or gold-tallow oxide compounds that do not release water under the reaction conditions, K and 2,2,6,6-tetramethylpyridine or phosphorus with a molecular weight higher than 500 (III) The compound acts as an additional stabilizer to carry out the polymer reaction. 2. The method as claimed in item 1 of the patent application includes preparing a olefin polymer using a solid-supported transition metal catalyst, which has been prepared to react an aluminum compound containing at least one alkyl group with the periodic table IV Group metal compounds. 3. A method as claimed in item 1 of the patent application, in which the catalyst is a complex compound on a carrier. 4. The method as claimed in item 1 of the patent application, in which hydrotalcite, zeolite or metal oxide compound or similar synthetic preparation which does not release water under reaction conditions after drying at 100 to 40,000 t is used Compound. 5. A method as claimed in item 1 of the patent application, which includes the use of a synthetically prepared hydrotalcite or zeolite. 6. The method as claimed in item 1 of the patent scope, in which hydrotalcite is of the general formula: Μ2 + ι-χ · Μ3 \ * (〇Η) 2 '(Α0 ·) ^ * mH20 ⑴ Where M 2 + is magnesium , Calcium, magnesium, barium, zinc, cadmium, lead, tin and / or nickel * Μ 3 is aluminum, boron or bismuth, -1-^^ 1 ίϋ m HI I a ^ i— i In \ J ^, va ( Please read the precautions on the back before filling out this page) The paper standard printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ABCD 821658 VI. Patent application scope A η is η Valence anion, (please read the weeping matters on the back and fill in this X) X is 0 to 0 · 5 * m is 0 to 2 > and A is -OH ·, Cl ·, Br. Γ · a〇4 'HCCV, CH3COO ·, C6H5COO ·, C032-, S042% COO coo-, (CHOHCOO) 22r. (CHOH) 4CH2OHCO〇-. C2H4 (COO) 22', CCH2C〇〇) 22-CH3CHOHCOO ', Si〇32 * , Si044 ·, Fe (CN) 63 *, Fe (CN) 64- or HP042-, or M ^ Al2 (0H) 2 …… .6llz (AnVmH20 (la) where M2 + is at least one gold of magnesium and zinc bars Magnesium is preferred. Eight 11- is C 0 3 2-, (gooyv, 0Η · and S2-series of Yin Li Η, η is the valence of anion, m is a positive number, X and ζ are positive numbers. 7 · As in the method of item 6 of the patent application range * where the metal is magnesium, X is the number of 2 to 6, z is the number less than 8. The method as claimed in item 1 of the patent application, where the zeolite is of the general formula Mx / nC (AIOz) x (Si〇2) y] * WH2〇 (X) Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Where n is the charge of the cation M, M is the element of the first or second main group of the periodic table, y: X is the number from 0.8 to 1.2, and w is the number from 0.5 to 10. 9. For example, the method of applying for the first item of the Patent Fan Garden 'includes the use of divalent metal oxides. -2-This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) S21658 A8 B8 C8 D8 VI. Scope of patent application 1 0. The method as claimed in item 1 of the scope of patent application, which includes the use of gold oxide oxide of the second main group or subgroup of the periodic table ° 1 1. The method as claimed in item 1, which includes the use of magnesium oxide or Zinc oxide. 1 2. The method as claimed in item 1 of the scope of patent application, wherein 2'2 '6,6-tetramethylpyridine with a molecular weight higher than 500 and containing at least one secondary monotriazine in its molecule is used as an additional Stabilizer. 1 3. The method as claimed in item 1 of the patent scope, wherein the following compound is used as an additional stabilizer — ------ :: clothing-(please read the precautions on the back before filling in this page) Order R Printed by the Ministry of Economy Central Standard Falcon Bureau Employee Consumer Cooperative%> 2500 RRII R-NH- (CH2 ) 3-N-(CH2) z ——N- (CH2) 3-NH-R 3- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) ABCD 321658 patent application park ch3 si one · 〇 I) 3 (CH2 M ,, > 1500 0 CH, Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1 4. The method as claimed in item 1 of the patent scope includes the use of phosphorus (III) compounds containing at least one p_〇-Ar group as an additional stabilizer, in which Ar is a monoalkyl phenyl, dialkyl phenyl or trialkyl phenyl 〇1 5. As in the patent application of the scope of the first item 'which includes the use of ginseng (2, 4 one two one three tertiary butyl Phenyl) phosphite or four bis (2 '4-two one three tertiary monobutyl phenyl) _4,4' _ secondary phenyl bisphosphinate as an additional stabilizer. 16. As in the method of patent application item 1, the steric barrier phenolic type antioxidant used therein is used as an additional stabilizer c 1 7. As in the application of patent application item 1, it includes the use of octadecyl β -(3,5-di-tertiary monobutyl-4-hydroxyphenyl) -propionate and 1,3,5-ginseng (3,5-ditritrimethylene-butyl-4 4-hydroxybenzyl ) A 2,4,6-trimethylbenzene as an additional stabilizer. 18. The method as described in item 1 of the patent application scope is to prepare a stable polypropylene. -4 This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297mm) I ------ installed ------ ordered (please read the precautions on the back before filling this page)