TW474941B - Method for improving hydrolysis resistance of pentaerythritol diphosphite and pentaerythritol diphosphite produced thereof - Google Patents

Abstract

The present invention relates to a method for improving the hydrolysis resistance of pentaerythritol diphosphite shown in formula (1) (in which R and R' can be the same or different and separately represent C4-C30 aliphatic or cycloaliphatic group or C6-C30 aryl or alkylaryl group, which are defined in the specification); which comprises adding a poor water soluble acid neutralizer into the pentaerythritol diphosphite shown in formula (1); and a pentaerythritol diphosphite prepared thereof.

Description

474941 V. Description of the invention (1) [Technical background] Pentaerythritol diphosphite (sometimes also referred to as phosphorus-containing antioxidant) is a kind of phosphorus-containing antioxidant with excellent performance, mainly used for polyethylene, polystyrene, polypropylene , ABS resin, etc. However, the pentaerythritol diacid vinegar itself is susceptible to the influence of environmental humidity or high water content of the plastic when it is manufactured, stored, or in the processing of plastics. Hydrolysis produces acidic substances, which accelerates its decomposition and reduces the antioxidant function. The decomposition of acidic materials will also damage the processing machine. To solve the above problems, as disclosed in U.S. Patent Nos. 3553298, 3787537, and 5342978, organic amine-based substances such as alkylamines, alkanolamines, pyrimidines, and anilines are added as hydrolysis-resistant stabilizers. Furthermore, U.S. Patent No. 5,208,362 discloses the addition of acid salts such as stearates, such as stearates, magnesium stearate, zinc stearate, and the like, which can be bonded to acidic substances. However, both methods can only improve the hydrolysis resistance of the phosphorus-containing antioxidant during storage. For processing conditions that contain a large amount of water during processing, the above-mentioned various additives still do not have a satisfactory effect. So far, the hydrolysis resistance of pentaerythritol diphosphite in processing has not reached the required standard, or although the stabilizer with strong alkalinity can stabilize the pentaerythritol diphosphite, the excessive alkalinity will destroy its function and make it resistant to Aging deteriorates. In view of this, it is still urgent to improve the hydrolysis resistance of pentaerythritol. The inventors have conducted intensive research and found that when a water-insoluble alkaline substance such as a metal hydroxide or a hydrate thereof, a silicate, or an aluminosilicate is added, pentaerythritol diphosphite having high overall hydrolysis resistance can be obtained. Its excellent water resistance can even be directly applied to the process of wet polymerization and polymerization.

474941

After the synthesis reaction is completed, the granulation can be directly extruded without drying in an oven, and the product hue and performance have no adverse effects, so the present invention is completed. [Detailed description] The present invention relates to a method for hydrolyzability: an improved pentaerythritol diphosphite of formula (I) resistant to och2 ch20 τ · / \ /, R—〇— p c 〇CH2 ch2〇

P—O—R / Formula (I) (wherein R and R may be the same or different, and each shows an aliphatic or cycloaliphatic group containing 4 to 30 carbon atoms or a group containing 6 to 30 carbon atoms Aryl or alkaryl is achieved by adding 1 to 100 parts by weight of a 'water-insoluble acid neutralizer to 100 parts by weight of pentaerythritol diphosphite. R and R in the formula (I) are aliphatic or Examples of the cycloaliphatic group include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, sarcoid, saponyl, heptadecyl, stearyl, arachid , Yushuji, lignan, etc .; the aryl group can be exemplified by phenyl, hexahydropyridyl, benzyl, hydrazinophenol, phenol, etc. The phenyl group is preferred. The alkylaryl group can be 1 to 3 Cs_1 (} alkyl-substituted aryl (the definition of aryl is the same as above). Examples of the alkyl group as a substituent include propyl, butyl, pentyl, hexyl, heptyl, octyl, quot; ^ &Quot; * In the compound of formula (1), it is preferred that 'R & R' is an aliphatic or cycloaliphatic group or an aryl group, and R and R 'are both stearyl, decyl, or triphenyl Tributylphenyl /

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The best is distearyl pentaerythritol. 5. Description of the invention (3) Mono-tert-butylphenyl is more preferable. "Nm :: difficult; r neutralizing agents include, for example, Shixi hydroxide, Shishi acid sodium, Shishi acid acid, magnesium Shishi acid, etc., can also be used in a variety of ways, such as bell dance, carbonate Town and its hydrates "j One or more of them are used in combination. The better is A silicon button capsule. ^ & Calcium and magnesium hydroxide or aluminum hydroxide. The best is sodium aluminosilicate or silicate. Mixture. For 100 parts by weight, add 30 to 60 parts by weight as a neutralizing agent. The added stem is 1 to 100 parts by weight. In the method, the age-based anti-aging agent may be added as the quaternary quaternary tetraol diphosphite vinegar. 0 to 100 parts by weight. 龄 The age-based antioxidant used in the present invention includes, for example, tetrafluorene, 'di-third-butyl-4, hydroxyphenyl) propionic acid] pentaerythritol, (_3,5 -Di-tertiary butyl-4, -hydroxyphenyl) propanoic stearyl ester, di (5 second butyl-4 -trimethyl-2-methylphenyl) butane, υ, 3_ di (5'-Third-butyl-4-hydroxy-2-fluorenylphenyl) butane, etc., using tetra [3 (3,5—second-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol vinegar as The amount of system oxidant added to the weight of 〇〇0 The pentaerythritol diphosphite is 0 to 100 parts by weight, and preferably 40 to 100 parts by weight. Each component of the present invention can be kneaded into a product in the following ways, including a) using dry kneading The machine mixes the ingredients to a uniform state, b) granulates the mixture of the above ingredients using a dry granulator, c) first heats and melts the ingredients pentaerythritol diphosphite in a high-speed mixer, and then adds Water-insoluble acid neutralizer and / or actinide antioxidant and high speed

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Page 6 474941 V. Description of the invention (4) Mix well, then pour it into a steel flat pan and cool it quickly to make a flake product. D) Granulate by using an extruder. After the dry kneading machine is uniformly mixed, the temperature of the three heating belts of the extruder is set to a temperature that can melt them, so that the pentaerythritol diphosphite is melted in the plastic area of the extruder and neutralized with the acid. The agent and / or phenolic antioxidant are mixed uniformly, and then cooled by air cooling after passing through the die, and then the αα is cut into pellets by a centrifugal cutting blade. Considering that the product dust is harmful to health, the manufacturing method is preferably (b), (c) and (d). The best kneading method is c) tableting method and d) using extruder granulation. The hardness and preservation of the product obtained by these two methods are the best. The test method to evaluate the hydrolysis resistance of the product is as follows; Each 1 gram sample was placed in a 100 ml beaker, 50 ml of hot water at ioo ° C was added, and one of the beakers was baked in a 10 Gt oven for 45 minutes. Remove the beaker and quickly cool to room temperature, and measure its pH (pH value). The other beaker was immediately cooled to room temperature without being placed in the oven, and the same value was measured and measured. A pH value between 6 and 8 indicates excellent hydrolysis resistance. Comparative Example A 3 liter five-necked flask equipped with a high-speed stirrer, a nitrogen gas tube, and a temperature controller was preheated to 8 ITC, and 1750 g of distearyl pentaerythritol diphosphite vinegar was placed at 80 t and After melting under nitrogen, pour it into a pan cooled with 5 ° C ice water. After the melt was solidified, it was pulverized by a tablet machine to obtain granules. Example 1 The configuration of a high-speed stirrer, a nitrogen pipe and a temperature controller

474941 V. Description of the invention (5) A five-liter five-necked flask was preheated to 80 ° C, and 800 grams of distearyl pentaerythritol diphosphite and 800 grams of tetrakis (3- (3,5, -di- Tert-butyl-4'-hydroxyphenyl) propionic acid) pentaerythritol ester, 400 g of sodium aluminosilicate. Heat this mixture to 80 ° C, stir it evenly with a high-speed stirrer until it becomes a paste. 'Pour the melt into a pan cooled with 5 ° C ice water. After the melt is solidified, it is crushed by a tablet machine. Obtained 1996 g of distearyl pentaerythritol diphosphite, tetrakis (3-3,5, -di-third-butyl-4, -hydroxyphenyl) propyl) pentaerythritol ester, sodium aluminosilicate 8%) Evenly distributed flakes (yield 99.8%). The flake-shaped product had a pH of 6.6 after being tested by the above-mentioned method for evaluating hydrolysis resistance. Example 2 800 grams of distearyl pentaerythritol diphosphite and 800 grams of tetrakis (3- (3 ', 5'_di-third-butyl-4, _hydroxyphenyl) propionic acid) are quaternized The alcohol ester and 400 g of sodium aluminosilicate are placed in a high-speed kneading machine, and they are placed in the feeding funnel of the extruder. The extruder spoon is at 52 °, 6 ° i: 50 °, and The exit of the machine: 22 is the near-extrusion machine, and the screw speed is set to 30 revolutions per knife clock to obtain granular products. The = ρΗ value after testing by the method of hydrolysis performance is 7 3. The results are as follows: Example 3… ° The method of Example 2 was repeated, but eight + grams of ethylene distearylamine was used in place of 400 g of A sodium aluminosilicate and 100 g of Qu. Also Γ 克辛 铭 Sodium salt. After the emergence of the pupa, it was a granular product. The pH of the granular product was 7.1 after being obtained with the pupa. Test method of hydrolytic performance on page 8 C: \ Program Files \ Patent \ 15797.ptd 474941 V. Description of the invention (6) Example 4 The method of Example 2 was repeated, but 80 phosphite was changed to 860 grams, and A mixture of 300 mg of pentaerythritol dihydroxide and magnesium hydroxide was used to replace 408 * A lice alumina and 40 g of freight 4UD a gram of sodium oxalate sodium osmium. The product was a lumpy product. After receiving the tablets, its pH value is 6. Test method 5 using the method of water and energy. Repeat the method of Example 2, but change the 800 phosphite to ASfin VIII. Two ... η ΐίί 260 grams of aluminum hydroxide gram Πf400 grams of dream 18 sodium salt. The granules were obtained after extrusion: η After the method for evaluating the hydrolysis resistance was tested, the pH value was 6.6. Example 6 Example 2 was repeated Method 'but change 800 grams of distearyl pentaerythritol dilinoleate to _ grams' 1 replace 26 grams of sodium aluminosilicate with 26 () grams of material and 4 {) grams of emulsified magnesium mixture. A granular product was obtained after pressing out, and the granular product was tested by the above method for evaluating hydrolysis resistance , Its PH value is 6. 6. Example 7 This example illustrates the stability effect of the products obtained from Comparative Examples and Examples 1 to 6 in the process of Aβδ. The process of the ABS test product is as follows. Add 0.3PHR of (3 ', 5'-di-tert-butyl-4, phenylphenyl) stearyl propionate, dehydrate it by centrifugation, and then directly premix with the products obtained in the above examples, the latter The added amount is 0 · 〇6PHr. At this time, the tree C: \ Program Files \ Patent \ 15797.ptd Page 9 V. Description of the invention (7)-The water content of the fat is about 10 to 15%, and j α — ★ ^ Produced by direct granulation and dehydration = "After making the cymbals and pressing the granules multiple times, test them = color index, oxidation guide temperature, and anti-aging of the chess box, and use their values The change evaluates the stabilizing effect of the water-insoluble acid neutralizer on the distearyl pentaerythritol diidite acid ester and the degree of damage to the phenolic antioxidant. The results are shown in Table 1. As can be seen from Table 1, the present invention is produced by adding a water-insoluble acid neutralizer. . Its stability effect on the oxidation guide temperature as an index of oxidation resistance is higher than that of the comparative example at 21 ° C, which can generally reach above 2 2 3 ° C, and the better can reach 2 3 0 ° C. Above; the color difference of the test piece after the oven test is also the same. The color difference of the acid neutralizer is less than 45, which is lower than that of the non-added comparative example. In summary, it can be known that the product prepared by adding a suitable amount of a water-insoluble acid neutralizing agent according to the present invention, has a stable effect for polymer polymerization (such as ASS polymerization), and the oxidation guide temperature of the product obtained is increased. The color difference after the oven test is small, and its pH value also falls within the optimal pH range of 6.0 to 8.0, indicating that its hydrolysis resistance is superior. Table 1 Oxidation guide temperature of each product and changes in color difference and pH after oven test Sample type Leakage ratio Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 13 11 51 41 42 41 43 44 45 Oxidation guide temperature after oven test. C ** 214 229 231 228 228 223 228 pH before flood test * 3.1 8.1 8.2 「7.8 8.6 8.4 8.4 pH 値 after oven test * 2 6.6 7.3 7.1 6.6 6.6 6.6

C: \ Program Files \ Patent \ 15797.ptd Page 10 474941 V. Description of the invention (8) *: The test method is the same as the above method of hydrolysis resistance. ** •• Tested with a thermal balance. : Pass the product through the injection mechanism to obtain a standard test piece in a hot air circulation oven (1 80 ° C X 2 hours) to determine the change in its yellow index.

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Claims (1)

In the winter of February / February 6, the patent application method-a method for improving the hydrolysis resistance of pentaerythritol diphosphite of formula (I): CK2 CHz 〇,-p CP—O—R / formula (I) OCH2 CH2O: (In the formula, R and R ′ may be the same or different, respectively, showing that the aliphatic or cycloaliphatic group containing 4 to 30 carbon atoms or the aryl group or aryl moiety having 3 to 30 carbon atoms may be 1 To 3 (V1 () alkyl-substituted alkylaryl); is added to 100 parts by weight of pentaerythritol diphosphite, and 1 to 100 parts by weight of a water-insoluble acid neutralizer, which is a water-insoluble acid neutralizer谗 is selected from the group consisting of hydrogen hydroxide, hydroxide hydroxide, argon oxide, sodium sulfonate, sodium oxalate, magnesium oxalate, calcium oxalate, potassium calcium silicate, potassium potassium silicate, and One or more of the groups formed by aluminum carbonate town hydrates. 2. The method according to item 1 of the scope of patent application, wherein the amount of the water-insoluble acid neutralizing agent is 100% by weight of pentaerythritol diphosphite. To 60 parts by weight. 3. The method according to item 1 of the patent application range, wherein a phenolic antioxidant is additionally added, and the phenolic antioxidant is selected from the group consisting of four (3- (3, 5, -Di-Third-butyl-4'-hydroxyphenyl) propionic acid) Pentaerythritol ester, (g ,, 5, -Di-Third-butyl-4'-hydroxyphenyl) propanoic acid stearyl ester , 丨, Bu., —Third-butyl-4-hydroxy-2-methylphenyl) butane and 1,1,3-tris (5, -third-butyl-4-hydroxy-2-fluorenyl) Phenyl) butane groups. 4. The method according to item 3 in the patent claim, wherein the added amount of the phenolic antioxidant is 0 to 丨 〇 〇 重 to 100 parts by weight of pentaerythritol diphosphite. • If the scope of the patent application is the 3rd method (3- (3,5, -di-third method), wherein the phenolic antioxidant is an alcohol ester and its added amount, oblique group ~ 4 ~ hydroxyphenyl) propionic acid ) Pentaerythritol is 40 to 100 parts by weight. Pentaerythritol dilinoleate of 6 parts by weight. If the scope of the patent application is No. 丨, the acid S is intended to distearyl pentaerythritol. The pentaerythritol diamide is filled with 7. Such as the scope of the patent application is No. 3 Phosphite. The method in which the acid ester is distearyl pentaerythritol, in which the pentaerythritol diphosphite is tetrakis (3-(3,, 5, -di ~ ^ th alcohol diphosphite, phenolic antioxidant tetraol ester. ~ Butyl-4'-hydroxyphenyl) propanoic acid) pentapentyl 8 ·-a kind of method with the resistance to hydrolysis of the first quarter of the sixth patent method of the preparation of four. Alcohol diphosphite A: \ 15797.ptc Page 13