CN1699386A - Phosphonite compound, its preparation method and its application as a stabilizer - Google Patents

Abstract

A phosphonite-based compound of the following formula , n and m each being 1; r₁、R₂、R₃、R₄、R₅、R₆Each independently represents hydrogen or C₁－C₁₀An alkyl group; x is optionally substituted by C₁－C₆Alkyl substituted C₁－C₃Alkylene or sulfur. The application also discloses a preparation method of the series of compounds and application of the series of compounds as a stabilizer in the manufacture of polymers.

Description

Phosphonite compound, its preparation method and its application as a stabilizer

technical field

The present invention relates to a novel phosphonite compound, its preparation method and its application as a stabilizer, in particular to a phosphonous acid which can be added to a polymer as a stabilizer to prevent a large amount of oxidation of the polymer Esters.

Background technique

General polymers are often faced with undesired degradation due to factors such as heat and oxidation when they are manufactured and used. Therefore, stabilizers are generally added to polymers to prevent polymer degradation. Stabilizers that decompose by oxidation are called antioxidants.

Adding antioxidants to the polymer can avoid or delay the oxidation reaction and prolong the life of the polymer. Kinetic studies have shown that the oxidative decomposition of polymers is caused by a series of free radical reactions, that is, once a free radical is generated in the polymer, it will react with oxygen to generate another free radical, and start A series of chain reactions are initiated and the polymer is destroyed. According to research, the generation of free radicals that trigger oxidation reactions may be affected by light, heat or other mechanical external forces, or may be caused by the action of external free radicals.

In general, antioxidants are mainly divided into two types: primary antioxidants (or chain-terminating antioxidants) and secondary antioxidants (or hydroperoxide decomposition antioxidants). The primary antioxidant is mainly composed of phenols hindered in stereo space, or secondary aromatic amines, which can quickly react with peroxide radicals and terminate the free radical reaction at normal temperature; the previous secondary antioxidants are Mainly sulfides or phosphites, which can react with hydroperoxides via a heterogeneous dissolution reaction mechanism to produce free radical-free products.

In the production or preservation of polymers, the industry often mixes primary and secondary antioxidants in an appropriate ratio, so that the polymer can avoid oxidation in two different ways at the same time. According to research, the combined use of primary and secondary antioxidants can further enhance the antioxidant effect. In European Patent EP 0000354, it is disclosed that the combined use of substituted 6-phenoxy-diphenyl[c,e]-[1,2]oxaphosphonite and phenolic antioxidant can improve the antioxidant capacity.

However, there is still a disadvantage when primary and secondary antioxidants are used together, that is, the molecular weight of these antioxidants is not large, and they are easily decomposed or volatilized due to heat. Therefore, when they are added to polymers and used as stabilizers, Generally, there is a problem of poor thermal stability. For example, Double Bond Chemical Co., Ltd. uses its primary antioxidant Chinox 1010 (phenolic antioxidant) and secondary antioxidant Chinox 168 (phosphite antioxidant) to 1 : 4 mixed with each other, although good anti-oxidation effect can be obtained, but the thermal stability is poor, especially the weight loss of Chinox 168 to temperature is very large, when the temperature reaches 350 ℃, Chinox 168 will be completely decomposed. Therefore, when the primary antioxidant and the secondary antioxidant are used in combination, there is still something that cannot be used practically in the industry.

In the development of anti-oxidative decomposition stabilizers for polymers, in addition to the above, there have been many studies on phosphonite compounds, such as 6-benzene, which has been disclosed in British Patent Specification No. 1,256,180. Oxygen-dibenzo[c,e]-[1,2]oxophosphonite (6-phenoxy-dibenz[c,e][1,2]oxaphosphorine), 6 of German Patent No. DE2,034,887 -(2,6-di-tert-butyl-4-methylphenoxy)-diphenyl[c,e]-[1,2]oxaphosphonite (6-(2,6-ditert-butyl -4-methyl-phenoxy)-dibenz[c, e]-[1,2]-oxaphosphorine), and 6-(2,4-di-tert-butyl-octyl-phenoxy)-dibenz in US 4,276,232 Benzene[c,e]-[1,2]oxaphosphorine (6-(2,4-di-tert.-octyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorine) , and phosphonite compounds disclosed in EP 0223739, US 4,185,006, US 4,380,515, and US 4,661,440. Each of the aforementioned patents is hereby incorporated by reference into this application.

Although the above-mentioned phosphonite-based antioxidants may have better thermal stability than the aforementioned phenolic-based primary or phosphite-based secondary antioxidants due to their larger molecular weight, but due to the limited types available, so In the practical application of anti-oxidative decomposition type stabilizers for polymers, there is still a need to continue to develop different and novel compounds.

Contents of the invention

In order to obtain a stabilizer that has both the dual functions of phenolic antioxidant and phosphite antioxidant, and exhibits good heat resistance and anti-oxidation, the present inventors have developed a combination of phenoxy groups with relatively large molecular weight and phosphite The concept that the phosphonate group is designed in the same molecular structure; Therefore, the purpose of the present invention is to provide a novel phosphonite compound with the following chemical formula (I), which has both primary and secondary in its molecular structure. The effective structure (phenoxy group and phosphonite group) of secondary antioxidant can reach the function of primary and secondary antioxidant simultaneously, and because the phosphonite compound of the present invention has larger molecular weight (mainly from benzene The contribution of the oxygen group part), so compared with the previous primary and secondary antioxidants, its thermal stability can be improved.

n and m are each 1;

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ each represent hydrogen or C ₁ -C ₁₀ alkyl;

X is C ₁ -C ₃ alkylene optionally substituted by C ₁ -C ₆ alkyl, or sulfur.

In another aspect, the present invention also provides a process for the preparation of the compound of formula (I).

Furthermore, the compound of formula (I) of the present invention can be added to a polymer as a stabilizer, therefore, the present invention also provides a stabilizer for a polymer mainly comprising the compound of formula (I).

Detailed ways

According to the above, the present invention provides a compound with the following chemical formula (I):

In the chemical formula (I), n and m are each 1; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ each represent hydrogen or C ₁ -C ₁₀ alkyl; X is optionally C C ₁ -C ₃ alkylene substituted by ₁ -C ₆ alkyl, or sulfur.

According to the present invention, the synthesis of the phosphonite compounds of the chemical formula (I) can be carried out with reference to the conventional methods, especially esterification or transesterification, for example, by means of the following phosphonite compounds represented by the chemical formula (A) Phosphonate and the phenol represented by (B) (the phenol with a larger molecular weight having at least two phenoxy groups) react to remove HY, and the following reaction formula (n(A)+(B)→(I )+nHY) shows:

The definition of each substituent in the phenol represented by (B) is as above chemical formula (I), and Y in (A) represents a reactive group, such as halogen (especially Cl); alkoxyl; or substituted or unsubstituted phenoxy. In a specific embodiment of the present invention, the phosphonite (A1) whose Y is Cl is used as the reaction initiator.

Generally, the above synthesis reactions are carried out in a non-acidic (neutral or alkaline) environment. When carried out in a neutral environment, the preferred reaction temperature is between normal temperature and 150 ° C; and the provision of the alkaline environment can be achieved by the presence of a base selected from the following groups: amines (for example, three Ethylamine, pyridine, N, N-dimethylaniline, sodium carbonate, and combinations thereof. Preferably, these bases are configured in an inert solvent, such as an aprotic solvent, such as petroleum ether, toluene, di Toluene, methyl ethyl ketone, acetonitrile or ethyl acetate, etc. In addition, when using amines to provide an alkaline environment, an excess of amines can be used as a solvent at the same time. Relevant synthetic reactions can refer to the content of German Open Gazette No. 2,034,887.

The starting material used when preparing the compound of formula (I) of the present invention, i.e. phosphonite (A) and phenol (B) can be known and can be obtained by previous methods, such as phosphonite (A) The preparation of phenol can be referred to the content of German Publication No. 2,034,887; and the phenol (B) starting material can directly use commercially available products, for example, the following commercialized phenol (b1) is purchased from Taiwan Changchun Company, product name AO-40; (b2), (b3) were purchased from Great Lake Company, and the product names are LOWINOX CA22 and LOWINOX TBM-6. In a specific embodiment of the present invention, (b1) is used as the phenolic starting reactant.

The specific example of the phosphonite compound (I) synthesized by the present invention is that n and m are both 1, and X is propyl methylene, R ₁ and R ₄ are both methyl, and R ₂ and R ₆ are both is a tert-butyl group, and R ₃ and R ₅ are all hydrogen compounds (Ia), that is, 6-(4,4'-butylene-2-tert-butyl-5-methylphenol-2'-tert-butyl Base-5'-methylphenoxy-diphenyl[c,e]-[1,2]oxaphosphonite (6-(4,4'-butylidene-2-t-butyl-5-methylphenol -2'-t-butyl-5'-methylphenoxy)-dibenz[c, e]-[1,2]oxaphosphorine), (Ia) structural formula is as follows:

The thermal stability of this specific example is indeed better than that of the aforementioned secondary antioxidants, especially compared to the most commonly used Chinox 168 in the industry; in a nitrogen environment, when the temperature is as high as 400 ° C, the phosphonous acid The specific example of the ester compound still has 48% by weight.

In addition, the compound with chemical formula (I) of the present invention can be added in polymers as a stabilizer, therefore, the present invention also provides a stabilizer for polymers, which mainly includes the aforementioned compound of chemical formula (I) of the present invention ) novel phosphonite compounds.

When the compound of formula (I) of the present invention is added to the polymer as a stabilizer to make a polymer composition, based on the total weight of the composition, the preferred addition amount is 0.005 to 5% by weight (50 to 50,000 ppm). More preferably, 0.05-0.5% by weight (500-5000 ppm) of the compound of formula (I) of the present invention is added to the polymer. The stabilizer for polymers of the present invention mainly comprises a compound of formula (I), a specific example of which is (Ia) as described above.

The scope of application of the polymer stabilizer of the present invention includes polyolefin polymers such as polyethylene (PE), polypropylene (PP), and copolymers thereof, polystyrene and copolymers thereof, such as ABS, etc., polyamide , linear polyester, polyurethane, polycarbonate, elastomer, polyvinyl chloride, and combinations thereof. In some specific examples, the polymer stabilizer of the present invention is added to PP, PE, and ABS, and various physical property tests show that it has effective oxidation resistance and stabilizing effects.

The polymer stabilizer of the present invention, in addition to mainly including the phosphonite compound represented by chemical formula (I), may further include phenolic and/or phosphite antioxidants, and the result of combined use can also reach good Stabilizing (antioxidant) effect. Phenolic antioxidants can be, for example, Chinox 1010, Chinox 1076, or combinations thereof; and phosphite antioxidants, can be, for example, Chinox 618, Chinox 168, or combinations thereof.

Hereinafter, the present invention will be further described by means of specific embodiments, but these embodiments are only for illustration rather than limiting the present invention.

Example

Physical Performance Test

In the present invention, the instruments used to measure physical properties such as yellowing value (b=+yellow/-blue), melt index (MI, MeltIndex; unit is g/10min) and yellowness index (YI, Yellowness Index) value are The spectrophotometer produced by BYK Garden is Color-guide 45/0, and the standard test method used is ASTM D-1925. Those with higher b value and MI value in the test result represent more serious yellowing and decay . The extruder used is the SEX-45 type extruder manufactured by Taiwan Yuanshun Company.

Reagent specifications

(i) 6-chloro-dibenzo[c,e]-[1,2]oxaphosphorine (6-chloro-dibenz[c,e]-[1,2]oxaphosphorine): according to the German disclosure Synthesized in Gazette No. 2,034,887.

(ii) 4,4'-butylene bis(2-tert-butyl-5-methylphenol (4,4'-butylidenebis(2-t-butyl-5-methylphenol)); Changchun Chemical Company, trade name AO-40.

(iii) Chinox 1010 (product name): manufactured by Taiwan Double Bond Chemical Co. di-t-butyl-4-hydroxyhydrocinnamate) mathane).

(iv) Chinox 1076: Made by Taiwan Double Bond Chemical Company, scientific name is octadecyl 3-(3', 5'-di-tert-butyl-4'-hydroxyl-phenyl) propionate (octadecyl3-(3 ', 5'-di-t-butyl-4'-hydroxy-phenyl) propionate).

(v) Chinox 168: manufactured by Taiwan Double Bond Chemical Co., Ltd., its scientific name is tris(2,4-di-tert-butylphenyl)phosphite (tris(2,4-di-t-butylphenyl)phosphite).

(vi) Chinox 618: Made by Taiwan Double Bond Chemical Company, scientific name is cycloneopentanetetrayl bis(octadacylphosphite)).

(vii) Polypropylene (PP): manufactured by Taiwan Yongjia Company, model 2020.

(viii) Polyethylene (PE): Formosa 9003 manufactured by Formosa Plastics Corporation.

(ix) Propylene-butadiene-styrene terpolymer (ABS): manufactured by Taiwan Chimei Corporation, product name Chimei 757.

Synthesis example

6-(4,4'-butylene-2-tert-butyl-5-methylphenol-2'-tert-butyl-5'-methylphenoxy-diphenyl[c,e]-[1, 2] Preparation of oxaphosphonite:

46.95g (0.2mol) of 6-chloro-diphenyl[c,e]-[1,2]oxophosphonite, 84.26g of 4,4'-butylenebis(2-tert-butyl -5-Methylphenol, 120ml of triethylamine and 350ml of toluene are placed in the reaction vessel together, the temperature is controlled at 80°C, and the reaction time is 18 hours. After the reaction is completed, the solution is filtered, and the solution is placed in At 0°C, a compound crystallizes from toluene. The product of this synthesis is 6-(4,4'-butylene-2-tert-butyl-5-methylphenol-2'-tert-butyl- 5'-Methylphenoxy-diphenyl[c,e]-[1,2]oxaphosphonite, yield 90%, melting point range 75ρ5°C.

Stabilizer type

In the following application examples, several conventional antioxidants and the synthesis examples of the above-mentioned application are used alone or in combination to make stabilizers for polymers, and are added to polymers and mixed to form polymer compositions. A spectrophotometer is used to perform physical performance tests to evaluate the stabilization (antioxidation) effect of the synthesis examples of this application on polymers (whether used alone or in combination with other antioxidants). The definitions of the combinations of stabilizers (A to F) are as follows : (The following ratios are weight ratios)

A: Chinox 1076/Chinox 168＝1/2;

B: Chinox 1010/Chinox 168 = 1/4;

C: The synthetic example is used alone;

D: Synthesis example/Chinox 168＝1/1

E: synthetic example/Chinox 1010=1/1;

F: synthetic example/Chinox 168/Chinox 1010＝2/1/1;

G: Chinox 1076/Chinox 618＝1/2;

H: synthetic example/Chinox 618 = 1/1;

I: synthetic example/Chinox 1076=1/1;

J: Synthetic example/Chinox1076/Chinox 618=2/1/1.

Application example 1

100 parts of polypropylene particles, 1200ppm of calcium stearate (calculated by weight of polypropylene) and stabilizers B to F (respective amounts are listed in Table 1 and Table 2) were mixed. The above-mentioned various mixtures were successively extruded five times with a single-screw extruder at 230°C. Table 1 and Table 2 show the effectiveness tests of each stabilizer in preventing material yellowing and decay.

Result: It can be seen from Table 1 that the addition of the synthesis example of the present application makes polypropylene exhibit good color stability (the change in b value is small). The increase of melt index in Table 2 represents the degradation of polypropylene, and after multiple extrusions, the synthesis example of this application shows better stability.

Application example 2

100 parts of polyethylene particles, 1200 ppm of calcium stearate (calculated by weight of polyethylene) and stabilizers A to F (respective amounts are listed in Table 3 and Table 4) were mixed. The above-mentioned various mixtures were successively extruded five times with a single-screw extruder at 200°C. Table 3 and Table 4 also show the effectiveness test results of each stabilizer in terms of avoiding material yellowing and material crosslinking. Results: It can be seen from Table 3 and Table 4 that the addition of the synthesis example of the present application makes polyethylene exhibit excellent color and anti-aging stability.

Application example 3

Mix 100 parts of ABS resin particles with various stabilizers (types and amounts are shown in Table 5). The mixtures were mixed using a single screw extruder at a temperature of 220°C. Before the various mixtures were aged in an oven (180°C), the yellowness index was measured with a spectrophotometer. After the various mixtures were aged in the oven for 2 hours, the yellowness index was measured again to match the yellowness index before aging. For comparison, the test results are shown in Table 5.

Results: Table 5 shows that the synthesis examples of the present application exhibit good color stability in ABS resin.

Table 1 Stabilizer type Amount added (ppm) b value after several extrusions 0th time 1st the 3rd time 5th blank sample - -0.75 -0.11 1.22 2.54 B 500 -1.52 -1.02 -0.31 0.25 B 1000 -1.60 -1.19 -0.76 -0.27 C 500 -1.82 -1.68 -1.05 -0.91 C 1000 -1.85 -1.72 -1.34 -1.07 C 2000 -1.90 -1.82 -1.68 -1.52 D. 1000 -1.80 -1.70 -1.08 -0.92 E. 1000 -1.78 -1.70 -1.12 -0.95 f 1000 -1.80 -1.71 -1.15 -0.97

Table 2 Stabilizer type Amount added (ppm) MI value after several extrusions 0th time 1st the 3rd time 5th blank sample - 4.5 5.1 6.2 8.3 B 500 4.2 4.8 5.8 6.5 B 1000 4.1 4.6 5.3 5.6 C 500 3.2 3.3 3.6 4.0 C 1000 3.0 3.1 3.2 3.4 C 2000 3.0 3.1 3.1 3.2 D. 1000 3.1 3.2 3.4 3.8 E. 1000 3.1 3.2 3.4 3.7 f 1000 3.0 3.2 3.5 3.7

table 3 Stabilizer type Amount added (ppm) b value after several extrusions 0th time 1st the 3rd time 5th blank sample - -0.85 1.05 2.85 4.2 A 500 -1.29 -1.03 -0.4 -0.2 A 1000 -1.51 -0.87 0.77 1.66 B 500 -1.81 -1.69 -0.96 -0.78 B 1000 -2.48 -2.12 -1.02 -0.02 C 500 -2.32 -2.25 -1.66 -0.87 C 1000 -2.13 -2.21 -1.86 -1.07 C 2000 -2.25 -2.22 -2.02 -1.68 D. 1000 -2.26 -2.21 -1.75 -1.00 E. 1000 -2.18 -2.20 -1.76 -1.02 f 1000 -2.24 -2.21 -1.80 -1.05

Table 4 Stabilizer type Amount added (ppm) MI value after several extrusions 0th time 1st the 3rd time 5th blank sample - 0.25 0.19 0.12 0.10 A 500 0.25 0.2 0.15 0.14 A 1000 0.25 0.25 0.23 0.21 B 500 0.25 0.21 0.18 0.16 B 1000 0.25 0.25 0.23 0.20 C 500 0.25 0.25 0.23 0.21 C 1000 0.25 0.26 0.26 0.25 C 2000 0.25 0.26 0.25 0.25 D. 1000 0.25 0.25 0.24 0.23 E. 1000 0.25 0.25 0.25 0.26 f 1000 0.25 0.25 0.24 0.25

table 5 Stabilizer type Amount added (ppm) YI value after several extrusions Initial YI value YI value after aging for 2 hours Change in YI value (эYI) blank sample - 14 75 61 C 1000 11 52 41 G 1000 12 60 48 h 1000 12 57 45 I 1000 12 58 46 J 1000 11 55 44

In summary, the present invention has the advantage of the phosphonite compound of formula (I) that it contains primary antioxidant (phenoxy group) and secondary antioxidant (phosphonite group) on a single compound. The structure can play the functions of two types of effective antioxidant groups at the same time, and on the other hand, the phosphonite compound of the present application has a molecular weight larger than that of the previous primary or secondary antioxidants. Therefore, compared with the previous The primary or secondary antioxidant (especially Chinox 168) is less likely to be decomposed or volatilized by heat, that is, it has better thermal stability, so when it is added to the polymer as a stabilizer, it is not easy to transfer to dissipated on the surface of the polymer. And it can be seen from the above-mentioned application examples that when the stabilizer mainly comprising the phosphonite compound of chemical formula (I) is added to the polymer, it does have good oxidation resistance, so that the polymer can be stabilized no matter in b, MI or The performance on the YI value all showed excellent stability.

Although the present invention has been explained in detail by the above detailed description and preferred embodiments, the present invention should not be construed as being limited by the foregoing embodiments; equivalent change. Therefore, without departing from the spirit of the present invention, all simple equivalent changes made according to the scope of the patent application of the present invention should fall within the scope covered by the scope of the patent application of the present invention.

Claims (20)

1. A phosphonite compound is characterized in that: it has the following chemical formula (I):

n and m are each 1; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ each represent hydrogen or C ₁ -C ₁₀ alkyl; X is C ₁ -C ₃ alkylene optionally substituted by C ₁ -C ₆ alkyl, or sulfur. 2 . The phosphonite compound according to claim 1 , wherein X is methylene substituted by C ₁ -C ₆ alkyl. 3. The phosphonite compound as claimed in claim 2, characterized in that: X is propyl methylene, R _{and R} are all methyl, and _R and _R are all tert-butyl, And R ₃ and R ₅ are both hydrogen. 4. A stabilizer for polymers, characterized in that it mainly comprises the phosphonite compound according to claim 1. 5. The stabilizer for polymers according to claim 4, characterized in that: in the chemical formula (I), X is a methylene group substituted by a C ₁ -C ₆ alkyl group. 6. The stabilizer for polymers as claimed in claim 5, wherein X is propyl methylene. 7. The stabilizer for polymers as claimed in claim 4, wherein X is sulfur. 8. The stabilizer for polymers according to claim 4, characterized in that it is suitable for being added to polymers such as polyolefins, polystyrene or copolymers thereof. 9. The stabilizer for polymers according to claim 8, wherein the polymer is selected from polypropylene, polyethylene or combinations thereof. 10. The stabilizer for polymers according to claim 8, characterized in that: the polymer is an acrylonitrile-butadiene-styrene copolymer. 11. The stabilizer for polymers according to claim 4, characterized in that it is suitable for adding to polyurethane. 12. The stabilizer for polymers according to any one of claims 4 to 10, characterized in that it can further be used in combination with a phenolic antioxidant. 13. The stabilizer for polymers according to any one of claims 4 to 10, characterized in that it can further be used in combination with a phosphite-based antioxidant. 14. The stabilizer for polymers according to any one of claims 4 to 10, characterized in that it can be further used in combination with phenolic and phosphite antioxidants. 15. The stabilizer for polymers according to claim 12, characterized in that: the phenolic antioxidant is selected from Chinox 1010, Chinox 1076 or their combination. 16. The stabilizer for polymers according to claim 13, characterized in that: the phosphite antioxidant is selected from Chinox 618, Chinox 168 or their combination. 17. A method for preparing the phosphonite compound of claim 1, characterized in that it comprises the following steps: Make a kind of compound with following chemical formula (A1) and a kind of compound with chemical formula (B) react under non-acidic environment,

n and m are each 1; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ each represent hydrogen or C ₁ -C ₁₀ alkyl; X is C ₁ -C ₃ alkylene optionally substituted by C ₁ -C ₆ alkyl or sulfur. 18. The preparation method according to claim 17, wherein X is methylene substituted by C ₁ -C ₆ alkyl. 19. The preparation method according to claim 18, characterized in that: X is propyl methylene, R ₁ and R 4 are both methyl groups, R ₂ and R ₆ are both tert-butyl groups, and R ₃ and R ₆ are all tert-butyl groups. R ₅ are all hydrogen. 20. The preparation method according to claim 17, characterized in that: the reaction is carried out in an alkaline environment.