1-(Substituted phenyl)oxy-2,4-pentanedione compound or its salt and its application as PVC stabilizer

Abstract

The present invention discloses a 1-(substituted phenyl)oxy-2,4-pentanedione compound or a salt thereof and its use as a PVC stabilizer. The 1-(substituted phenyl)oxy-2,4-pentanedione compound has the structure represented by formula (I): #imgabs0#, wherein R is H or an electron-donating group, and R is connected to the benzene ring in an ortho-, meta-, or para-substituted manner or in a benzo-binding manner. When used as a PVC stabilizer, the 1-(substituted phenyl)oxy-2,4-pentanedione compound or a salt thereof of the present invention exhibits outstanding thermal stability and weather resistance, effectively improving the weather resistance of PVC products and the thermal stability during processing.

Description

Technical Field

[0001] The present invention belongs to the technical field of PVC stabilizers, and in particular relates to a 1-(substituted phenoxy)oxy-2,4-pentanedione compound or a salt thereof and application thereof as a PVC stabilizer. Background Art

[0002] Polyvinyl chloride (PVC) is a polymer material obtained through the addition polymerization of vinyl chloride. It is the third most widely produced synthetic plastic after polyethylene and polypropylene. Due to its heat and fire resistance, chemical resistance, and excellent insulation properties, PVC is widely used in products across various industries. However, PVC has poor thermal stability and UV resistance. During the PVC processing and molding process, heating PVC at around 200°C breaks a large number of C-Cl bonds, producing HCl. HCl catalyzes the further decomposition of PVC, leading to the formation of numerous C=C double bonds in the molecular chain. Alternatively, under the action of ultraviolet light, free radicals are generated, causing the color of PVC to gradually change from its original white color to yellow, orange, and finally brown, affecting the product's color. Furthermore, heat or light can also break the molecular chains of PVC, significantly degrading its performance. PVC mixtures also exhibit a high coefficient of friction between PVC and metal surfaces within the processing temperature range. Therefore, a variety of chemical additives are required for PVC materials, such as PVC heat stabilizers, HCl absorbers, and lubricants.

[0003] There are many types of PVC heat stabilizers. Commonly used domestically and internationally include lead salt composite stabilizers, organotin stabilizers, metal soap stabilizers, organic-based stabilizers, calcium-zinc, barium-zinc, and potassium-zinc composite stabilizers. Lead salt stabilizers are inexpensive and offer excellent performance, but they are highly toxic to the environment and humans. Although once used in large quantities, they are no longer an ideal choice for today's green production requirements. Organotin stabilizers are cumulatively toxic. Although added in small amounts, they are expensive, limiting their application. Metal soap stabilizers are less effective when used alone and require adjuvants. Calcium-zinc stabilizers react with PVC to form zinc chloride, which strongly catalyzes the degradation of PVC, causing it to turn black. Furthermore, calcium-zinc stabilizers can precipitate from the PVC after prolonged use, causing scaling and decreased stability. Barium-zinc stabilizers are also less commonly used due to their high price. In summary, traditional PVC stabilizers all have their drawbacks. Furthermore, traditional PVC stabilizers have poor compatibility with PVC and can precipitate after prolonged use, affecting the appearance and performance of the PVC.

[0004] In recent years, β-diketone compounds, especially stearylbenzoylmethane (SBM) and dibenzoylmethane (DBM), have played an active role in PVC stabilizers as auxiliary thermal stabilizers. However, both have obvious application defects. For example, SBM has poor thermal stability but good UV resistance (commonly known as weather resistance); while DBM has good thermal stability but poor weather resistance. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above technical deficiencies, propose a 1-(substituted phen)oxy-2,4-pentanedione compound or its salt and its use as a PVC stabilizer, and solve the technical problems of insufficient thermal stability and weather resistance of PVC stabilizers in the prior art.

[0006] In a first aspect, the present invention provides a 1-(substituted phenyl)oxy-2,4-pentanedione compound or a salt thereof, wherein the 1-(substituted phenyl)oxy-2,4-pentanedione compound has a structure shown in formula (I):

[0007]

[0008] Wherein, R is H or an electron-donating group, and R is connected to the benzene ring in an ortho-, meta-, or para-substituted manner or in a benzo-bonded manner.

[0009] In a second aspect, the present invention provides use of the above-mentioned 1-(substituted phen)oxy-2,4-pentanedione compound or a salt thereof as a PVC stabilizer.

[0010] In a third aspect, the present invention provides a PVC stabilizer composition, comprising at least one of the 1-(substituted phen)oxy-2,4-pentanedione compounds or salts thereof provided in the first aspect of the present invention.

[0011] Compared with the prior art, the present invention has the following beneficial effects:

[0012] When used as a PVC stabilizer, the 1-(substituted phenoxy)oxy-2,4-pentanedione compound or its salt has outstanding performance in both thermal stability and weather resistance, and can effectively improve the weather resistance of PVC products and the thermal stability during processing. DETAILED DESCRIPTION

[0013] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0014] The present invention conducts beneficial design and modification as well as performance research experiments based on the structure of existing β-diketone compounds, and discovers a new class of 1-(substituted phen)oxy-2,4-pentanedione compounds or their salts. When used as PVC stabilizers, they have both good thermal processing properties and good UV resistance, and play a positive role in promoting the development of PVC stabilizers.

[0015] Based on this, the present invention is proposed.

[0016] In a first aspect, the present invention provides a 1-(substituted phenyl)oxy-2,4-pentanedione compound or a salt thereof, wherein the 1-(substituted phenyl)oxy-2,4-pentanedione compound has a structure shown in formula (I):

[0017]

[0018] Wherein, R is H or an electron-donating group; further, R includes but is not limited to H, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 substituted or unsubstituted amino, substituted or unsubstituted benzene ring, substituted or unsubstituted pyridine ring, etc.; further, R includes but is not limited to H, halogen substituted or unsubstituted C 1-6 Alkyl, halogen substituted or unsubstituted C 1-6 Alkoxy, C 1-6 Alkyl substituted or unsubstituted amino group, benzene ring, C 1-6 Alkyl, C 1-6 Alkoxy or halogen substituted benzene ring, pyridine ring, C 1-6 Alkyl, C 1-6 The R group is substituted at the ortho, meta, or para position or is connected to the benzene ring in a benzo-bonded manner.

[0019] In some specific embodiments of the present invention, the above-mentioned 1-(substituted phenoxy)oxy-2,4-pentanedione compound is: 1-phenoxy-2,4-pentanedione, 1-(4-ethylphenoxy)oxy-2,4-pentanedione, 1-(2-butoxyphenoxy)oxy-2,4-pentanedione, 1-(3-N,N-dimethylaminophenoxy)oxy-2,4-pentanedione, 1-(4-aminophenoxy)oxy-2,4-pentanedione, 1-(β-naphthyl)oxy-2,4-pentanedione, 1-(8-isoquinoline)oxy-2,4-pentanedione, and 1-[(4-(2-chlorophenoxy)]oxy-2,4-pentanedione.

[0020] In this embodiment, the salt of the 1-(substituted phenoxy)oxy-2,4-pentanedione compound has a structure represented by formula (II):

[0021]

[0022] Wherein, M is a calcium ion or a zinc ion.

[0023] In some specific embodiments of the present invention, the salt of the 1-(substituted phenoxy)oxy-2,4-pentanedione compound is a calcium salt or zinc salt of the following 1-(substituted phenoxy)oxy-2,4-pentanedione compounds: 1-phenoxy-2,4-pentanedione, 1-(4-ethylphenoxy)oxy-2,4-pentanedione, 1-(2-butoxyphenoxy)oxy-2,4-pentanedione, 1-(3-N,N-dimethylaminophenoxy)oxy-2,4-pentanedione, 1-(4-aminophenoxy)oxy-2,4-pentanedione, 1-(β-naphthyl)oxy-2,4-pentanedione, 1-(8-isoquinolinyl)oxy-2,4-pentanedione, and 1-[(4-(2-chlorophenoxy)]oxy-2,4-pentanedione.

[0024] In this embodiment, the preparation method of the above-mentioned 1-(substituted phen)oxy-2,4-pentanedione compound or its salt comprises the following steps:

[0025] S1, preparing 1-(substituted phenoxy) acetic acid ester and acetone by Claisen condensation method to obtain 1-(substituted phenoxy) oxy-2,4-pentanedione compound; and, optionally,

[0026] S2. Under alkaline conditions, 1-(substituted phenyl)oxy-2,4-pentanedione compound is added to an aqueous solution containing calcium ions and / or zinc ions. After the reaction, the solution is filtered, washed, and dried to obtain a salt of the 1-(substituted phenyl)oxy-2,4-pentanedione compound.

[0027] The specific reaction route is as follows:

[0028]

[0029] Where n is 0 or 1.

[0030] The base is at least one of ammonia water and alkaline metal hydroxide.

[0031] In some specific embodiments of the present invention, 1-(substituted phen)oxyacetic acid ester is obtained by reacting substituted phenol with chloroacetic acid ester. The specific reaction formula is as follows:

[0032]

[0033] Where n is 0 or 1.

[0034] In a second aspect, the present invention provides use of the above-mentioned 1-(substituted phen)oxy-2,4-pentanedione compound or a salt thereof as a PVC stabilizer.

[0035] When the 1-(substituted phenoxy)oxy-2,4-pentanedione compound or its salt is used as a PVC stabilizer, it performs well in tests on PVC thermoforming processing and weather resistance, outperforming reference materials SBM or DBM, and is green, environmentally friendly, and safe.

[0036] In a third aspect, the present invention provides a PVC stabilizer composition, comprising at least one of the 1-(substituted phen)oxy-2,4-pentanedione compounds or salts thereof provided in the first aspect of the present invention.

[0037] In the present invention, the PVC stabilizer composition can be formed by combining one or more of the above-mentioned 1-(substituted phenoxy)oxy-2,4-pentanedione compounds or their salts, or by combining one or more of the above-mentioned -(substituted phenoxy)oxy-2,4-pentanedione compounds or their salts with other stabilizers (such as lead salt composite stabilizers, organotin stabilizers, metal soap stabilizers, organic-based stabilizers, calcium zinc, barium zinc, potassium zinc composite stabilizers, etc.), and the present invention is not limited to this.

[0038] In some preferred embodiments of the present invention, the PVC stabilizer composition comprises a mixture of 1-phenoxy-2,4-pentanedione and 1-(β-naphthyl)oxy-2,4-pentanedione calcium.

[0039] In the present invention, the PVC stabilizer can be mixed with other substances (including PVC), and these other substances include but are not limited to: PVC, zinc stearate, hydrotalcite, zeolite, calcium carbonate, other additives, etc.

[0040] In this embodiment, the amount of the PVC stabilizer composition is 1%-5% of the total mass of the PVC.

[0041] Example 1: Preparation of 1-phenoxy-2,4-pentanedione (1)

[0042]

[0043] Under ice-cooling, 13.4 g of potassium tert-butoxide was added to 150 ml of THF, and 7.0 g of acetone was added dropwise with stirring. Subsequently, 16.6 g of methyl 1-phenoxyacetate was added, and the reaction was continued, followed by TLC analysis. After the reaction, THF was evaporated under reduced pressure, and the residue was added to 100 ml of ice water and extracted twice with 30 ml of ethyl acetate. The oil layers were combined and washed twice with 30 ml of water. The ethyl acetate layer was dried over an appropriate amount of anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure to obtain 13.9 g of a white low-melting solid with a yield of 72.2%. MS (m / z, ESI + ): 192.01[M] + .

[0044] Example 2: Preparation of 1-(4-nitrophenyl)oxy-2,4-pentanedione (2)

[0045]

[0046] Under ice bath, NaH 10.0g is added in DMF 50ml, and acetone 12.0g is added dropwise with stirring. Subsequently, 1-(4-nitrobenzene) oxygen base-methyl acetate 27.0g is added, drip and finish, and the reaction is continued at room temperature, and TLC is monitored. After reaction, saturated sodium chloride aqueous solution 100ml is added to quench the reaction, and 100ml of dichloromethane is extracted 2 times. Subsequently, saturated aqueous common salt solution 100ml is washed with oil layer 2 times, appropriate amount of Na2SO4 is dried dichloromethane layer, and solvent is evaporated. Residue adds petroleum ether 20ml and precipitates out a large amount of yellow solid, filters, and is dried. The crude product is dissolved with a small amount of hot n-hexane and recrystallized to obtain 22.7g of light yellow crystalline powder, yield 75.0%. 1 HNMR(CDCl3): δ8.10-7.98(m,2H),7.14-7.05(m,2H),5.15(s,J=7.4Hz,2H),3.63-3.58(s,2H),2.25-2.11(s,3H); MS(m / z, ESI+): 237.33[M] + .

[0047] Example 3: Preparation of 1-(2-carboxylic acid phenyl)oxy-2,4-pentanedione (3)

[0048]

[0049] Referring to the method and dosage of compound (2), 20.4 g of light yellow crystalline powder was obtained with a yield of 67.5%. 1 H NMR(CDCl3): δ12.8-7.98(m,2H),7.85-7.61(m,H),7.60-7.47(m,H),7.40-6.9 7(m,2H),5.05-4.81(s,2H),3.71-3.60(s,2H),2.41-2.22(s,3H);MS(m / z,ESI + ): 237.33[M+1] + .

[0050] Example 4: Preparation of 1-(4-ethylphenoxy)oxy-2,4-pentanedione (4)

[0051]

[0052] Referring to the method and dosage of compound (1), 15.0 g of colorless oil was obtained with a yield of 80.2%. 1H NMR(CDCl3): δ7.22-7.01(m,2H),6.91-6.80(m,2H),5.08(s,2H),3.60-3.44 (s,2H),2.80-2.72(m,2H),2.28-2.17(s,3H),1.40-1.22(m,3H);MS(m / z,ESI + ): 220.45[M] + .

[0053] Example 5: Preparation of 1-(2-butoxyphen)oxy-2,4-pentanedione (5)

[0054]

[0055] Referring to the method and dosage of compound (1), 13.3 g of white solid was obtained with a yield of 72.4%. 1 H NMR(CDCl3): δ7.02-6.73(m,4H),5.35-5.21(s,2H),4.37-4.24(m,2H),3.71-3.60(s,2H) ,2.49-2.28(m,3H),1.88-1.74(m,2H),1.55-1.47(m,2H),1.11-0.97(m,3H); MS(m / z,ESI + ): 264.51[M] + .

[0056] Example 6: Preparation of 1-(3-N,N-dimethylaminophenyl)oxy-2,4-pentanedione (6)

[0057]

[0058] Under ice-cooling, add 3.6 g of sodium amide to 100 ml of toluene, and add 12.0 g of acetone dropwise with stirring. Subsequently, add 16.4 g of methyl 1-(3-N,N-dimethylaminophenyl)oxyacetate, and continue the reaction at 60°C. TLC analysis is performed. After completion of the reaction, the solvent is evaporated under reduced pressure, and the residue is added to 100 ml of ice water and filtered. The filter cake is washed with ethanol, dried, and recrystallized from chloroform to obtain 15.5 g of a light yellow solid powder (83.5% yield). 1 H NMR (d6-DMSO): δ7.23-7.19(m,1H),6.48-6.26(m,3H),5.07-4.99(s,2H),3.34-3.20(s,2H),2.97-2.64(s,6H),2.44-2.35(m,3H); MS(m / z, ESI + ):235.38[M] + .

[0059] Example 7: Preparation of 1-(4-aminophenyl)oxy-2,4-pentanedione (7)

[0060]

[0061] By referring to the preparation method and dosage of compound (6), 14.6 g of light yellow solid powder was obtained with a yield of 76.6%. 1 HNMR(d6-DMSO): δ7.01-6.67(m,4H),5.54(d,2H),5.13-5.07(m,2H),3.62-3.49(m,2H),2.41-2.20(m,3H); MS(m / z, ESI + ):207.22[M] + .

[0062] Example 8: Preparation of 1-(β-naphthyl)oxy-2,4-pentanedione (8)

[0063]

[0064] Under ice-cooling, 14.7 g of sodium isopropoxide was added to 90 ml of isopropanol, and 8.8 g of acetone was added dropwise with stirring. Subsequently, 16.6 g of methyl 1-(β-naphthyl)oxyacetate was added portionwise, and the reaction was carried out at -5°C. TLC was performed. After the reaction, the isopropanol was evaporated under reduced pressure, and the residue was added to 100 ml of ice water and extracted twice with 30 ml of ethyl acetate. The oil layers were combined and washed twice with 30 ml of water. The ethyl acetate layer was dried over an appropriate amount of anhydrous calcium chloride, filtered, and the solvent was removed under reduced pressure to obtain 13.7 g of a white solid powder (yield 73.6%). 1 H NMR(CDCl3): δ7.95-7.61(m,3H),7.53-7.25(m,3H),5.31-5.25(m,2H),3.77-3.64(m,2H),2.37-2.24(m,3H); MS(m / z, ESI + ): 242.38[M] + .

[0065] Example 9: Preparation of 1-(8-isoquinolinyl)oxy-2,4-pentanedione (9)

[0066]

[0067] By referring to the preparation method and dosage of compound (6), 12.6 g of light yellow crystalline powder was obtained with a yield of 68.7%. 1HNMR(d6-DMSO): δ9.78-9.64(m,1H),8.55-8.41(m,1H),7.94-6.87(m,3H),5.54-5.39(m,2H),3.86-3.65(m,2H),2.44-2.30(m,3H); MS(m / z, ESI + ): 244.22[M+1] + .

[0068] Example 10: Preparation of 1-[(4-(2-chlorophenyl)]oxy-2,4-pentanedione (10)

[0069]

[0070] Referring to the method and dosage of compound (2), 25.2 g of light yellow crystalline powder was obtained with a yield of 85.2%. 1 H NMR (CDCl3): δ7.81-7.58(m,3H),7.43-7.27(m,3H),7.02-6.89(m,2H),5.32-5.19(m,2H),3.66-3.44(m,2H),2.57-2.41(m,3H); MS(m / z, ESI + ): 302.58[M] + .

[0071] Example 11: Preparation of 1-phenoxy-2,4-pentanedione zinc (11)

[0072]

[0073] 13.9 g of 1-phenoxy-2,4-pentanedione was dispersed in 50 ml of 30% ammonia water, and 4.9 g of zinc chloride was added. Stirring was continued for 30 min to produce a large amount of white precipitate. The precipitate was filtered, washed with water and methanol in sequence, and dried to obtain 15.3 g of white solid powder with a yield of 95.3%.

[0074] Example 12: Preparation of 1-(3-N,N-dimethylaminophenyl)oxy-2,4-pentanedione zinc (12)

[0075]

[0076] 15.6 g of 1-(3-N,N-dimethylaminophenyl)oxy-2,4-pentanedione was dispersed in 50 ml of 20% NaOH aqueous solution, and 3.2 g of zinc chloride was added. Stirring was continued for 30 min to produce a large amount of white precipitate. The precipitate was filtered, washed with water and acetone, and dried to obtain 17.4 g of white solid powder with a yield of 98.2%.

[0077] Example 13: Preparation of 1-(β-naphthyl)oxy-2,4-pentanedione calcium (14)

[0078]

[0079] Disperse 15 g of 1-(β-naphthyl)oxy-2,4-pentanedione in 100 ml of 5% NaOH aqueous solution, add 5.0 g of calcium hydroxide, and continue stirring for 30 minutes to produce a large amount of white precipitate. Filter, wash with water and methanol in sequence, and dry to obtain 15.6 g of white solid powder with a yield of 96.6%.

[0080] Example 14: Preparation of 1-[(4-(2-chlorophenyl)]oxy-2,4-pentanedione zinc (15)

[0081]

[0082] 22 g of 1-[(4-(2-chlorophenyl)]oxy-2,4-pentanedione was dispersed in 50 ml of a 10% aqueous solution of NaOH, and 5.0 g of zinc hydroxide was added. The mixture was stirred for 30 min to produce a large amount of white precipitate. The precipitate was filtered, washed with water and acetonitrile, and dried to obtain 22.2 g of a white solid powder with a yield of 91.3%.

[0083] Application Example 1: Preparation of PVC compound containing 1-(2-carboxyphenyl)oxy-2,4-pentanedione as a single component

[0084] 30 g of 1-(2-carboxylic acid phenyl)oxy-2,4-pentanedione, 5 g of polyacrylate (ACR), 15 g of titanium dioxide, 200 g of calcium carbonate, and 1000 g of PVC were mixed in a high-speed mixer at 110° C. for 1 hour and set aside.

[0085] Application Example 2: Preparation of PVC compound containing single component calcium 1-(4-ethylphenyl)oxy-2,4-pentanedione

[0086] Mix 20 g of 1-(4-ethylphenyl)oxy-2,4-pentanedione calcium, 5 g of ACR, 15 g of titanium dioxide, 200 g of calcium carbonate, and 1000 g of PVC in a high-speed mixer at 110° C. for 1 hour and set aside.

[0087] Application Example 3: Preparation of a two-component PVC compound containing 1-phenoxy-2,4-pentanedione and 1-(β-naphthyl)oxy-2,4-pentanedione calcium

[0088] Mix 15 g of 1-phenoxy-2,4-pentanedione and 15 g of calcium 1-(β-naphthyl)oxy-2,4-pentanedione with 5 g of ACR, 15 g of titanium dioxide, 200 g of calcium carbonate, and 1000 g of PVC in a high-speed mixer at 110° C. for 2 h and set aside.

[0089] Application Example 4: Preparation of a two-component PVC compound containing zinc 1-phenoxy-2,4-pentanedione and calcium 1-(3-N,N-dimethylaminophenyl)oxy-2,4-pentanedione

[0090] Mix 15 g of 1-(3-N,N-dimethylaminophenyl)oxy-2,4-pentanedione calcium, 5 g of ACR, 15 g of titanium dioxide, 200 g of calcium carbonate, and 1000 g of PVC in a high-speed mixer at 110°C for 30 minutes, then add 15 g of 1-phenoxy-2,4-pentanedione zinc and continue mixing for 1 hour, and then set aside.

[0091] Application Example 5: Preparation of a PVC mixture containing 1-phenoxy-2,4-pentanedione, calcium 1-phenoxy-2,4-pentanedione, and zinc 1-phenoxy-2,4-pentanedione

[0092] Mix 10 g of 1-phenoxy-2,4-pentanedione with 5 g of ACR, 15 g of titanium dioxide, 200 g of calcium carbonate, and 1000 g of PVC in a high-speed blender at 110°C for 30 minutes, then add 10 g of calcium 1-phenoxy-2,4-pentanedione and continue mixing for 30 minutes. Finally, add 10 g of zinc 1-phenoxy-2,4-pentanedione and mix for 1 hour, and then set aside.

[0093] Application Example 6: Preparation of a PVC mixture containing calcium 1-(4-aminophenyl)oxy-2,4-pentanedione, calcium 1-(8-isoquinolinyl)oxy-2,4-pentanedione, and zinc 1-[(4-(2-chlorophenyl)]oxy-2,4-pentanedione)

[0094] 10 g of 1-(4-aminophenyl)oxy-2,4-pentanedione calcium was mixed with 5 g of ACR, 15 g of titanium dioxide, 200 g of calcium carbonate, and 1000 g of PVC in a high-speed mixer at 110°C for 30 min. 10 g of 1-(8-isoquinolinyl)oxy-2,4-pentanedione calcium was added and the mixture was mixed for another 30 min. Finally, 10 g of 1-[(4-(2-chlorophenyl)]oxy-2,4-pentanedione zinc was added and the mixture was mixed for 1 h before use.

[0095] experimental group

[0096] During the processing of PVC, stabilizers must be added. The stabilizers should not only be lighter in color, not affect the overall color of PVC, and have no obvious irritating smell, but also enhance the weather resistance and high thermal stability of PVC, making PVC better during processing and use. The specific test method is as follows:

[0097] One (30g) or more than one 1-(substituted-phen)oxy-2,4-pentanedione compound or salt thereof (combined in a 30g evenly divided mass ratio), 5g ACR, 15g titanium dioxide, 200g calcium carbonate, and 1000g PVC were ground and mixed thoroughly. The mixture was then pressed into sheets using a Harp rheometer (RM-200A). After 7 minutes, the sheets were cut and cooled to room temperature to produce the finished PVC. The initial hue of the extruded sheets was measured using a colorimeter (Konica Minolta CR-10). Alternatively, the cut sheets were placed in a QUV weathering instrument (Q-LAB, USA) and measured every 24 hours. The results are expressed as L, a, and b values. The results were compared with single-component or two-component mixtures containing SBM or DBM. The test results are summarized in Table 1.

[0098] Table 1 Initial hue and weather resistance of one or more compositions of 1-(substituted phen)oxy-2,4-pentanedione compounds or their salts

[0099]

[0100]

[0101] (The thermal stability and weather resistance of PVC products are mainly judged by the b value. The smaller the b value, the better the thermal stability and weather resistance)

[0102] The above experimental results show that, with the exception of 1-(4-nitrophenyl)oxy-2,4-pentanedione and 1-(2-carboxyphenyl)oxy-2,4-pentanedione, the thermal stability and weather resistance of other 1-(substituted phenyl)oxy-2,4-pentanedione compounds are superior to or equivalent to SBM and DBM, overcoming the problem that existing β-diketone compounds (SBM and DBM) cannot achieve both good thermal stability and weather resistance as auxiliary thermal stabilizers. Experimental results on 1-(substituted phenyl)oxy-2,4-pentanedione compounds containing carboxyl and nitro groups show that compared with DBM or SBM, compounds with electron-withdrawing groups (such as nitro and carboxyl groups) on the benzene ring substituents exhibit poor thermal stability and weather resistance. However, single-component, two-component, and three-component 1-(substituted phenyl)oxy-2,4-pentanedione compounds containing electron-donating groups not only show improved weather resistance but also exhibit good thermal stability. The inventors also unexpectedly discovered that a combination of 1-phenoxy-2,4-pentanedione and 1-(β-naphthyl)oxy-2,4-pentanedione calcium exhibits improved thermal stability and weather resistance compared to either 1-phenoxy-2,4-pentanedione or 1-(β-naphthyl)oxy-2,4-pentanedione calcium alone. Therefore, 1-(substituted phenoxy)oxy-2,4-pentanedione compounds or their salts exhibit excellent application value as PVC stabilizers.

[0103] The specific embodiments of the present invention described above do not limit the scope of protection of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the scope of protection of the claims of the present invention.

Claims

1. A 1-(substituted phenyl)oxy-2,4-pentanedione compound, characterized in that: The 1-(substituted phenyl)oxy-2,4-pentanedione compound is one of 1-(4-ethylphenyl)oxy-2,4-pentanedione, 1-(2-butoxyphenyl)oxy-2,4-pentanedione, 1-(3-N, N-dimethylaminophenyl)oxy-2,4-pentanedione, 1-(4-aminophenyl)oxy-2,4-pentanedione, 1-(β-naphthyl)oxy-2,4-pentanedione, 1-(8-isoquinolinyl)oxy-2,4-pentanedione, and 1-[(4-(2-chlorophenyl)]oxy-2,4-pentanedione.

2. A salt of a 1-(substituted phenyl)oxy-2,4-pentanedione compound, characterized in that: It has the structure shown in formula (II): ； Wherein, R is H, halogen substituted or unsubstituted C 1-6 Alkyl, halogen substituted or unsubstituted C 1-6 Alkoxy, C 1-6 Alkyl substituted or unsubstituted amino group, benzene ring, C 1-6 Alkyl, C 1-6 Alkoxy or halogen substituted benzene ring, pyridine ring, C 1-6 Alkyl, C 1-6 At least one of the pyridine rings substituted with an alkoxy group or a halogen, and R is connected to the benzene ring in an ortho, meta, para substitution or benzo combination manner, and M is a calcium ion or a zinc ion.

3. The salt of the 1-(substituted phenyl)oxy-2,4-pentanedione compound according to claim 2, characterized in that The salt of the 1-(substituted phenyl)oxy-2,4-pentanedione compound is a calcium salt or zinc salt form of the following 1-(substituted phenyl)oxy-2,4-pentanedione compounds: 1-phenoxy-2,4-pentanedione, 1-(4-ethylphenyl)oxy-2,4-pentanedione, 1-(2-butoxyphenyl)oxy-2,4-pentanedione, 1-(3-N, N-dimethylaminophenyl)oxy-2,4-pentanedione, 1-(4-aminophenyl)oxy-2,4-pentanedione, 1-(β-naphthyl)oxy-2,4-pentanedione, 1-(8-isoquinolinyl)oxy-2,4-pentanedione, and 1-[(4-(2-chlorophenyl)]oxy-2,4-pentanedione.

4. A method for preparing a salt of a 1-(substituted phenyl)oxy-2,4-pentanedione compound according to any one of claims 2 to 3, comprising the following steps: 1-(substituted phenyl)oxy-2,4-pentanedione was prepared by reacting 1-(substituted phenyl)oxyacetate with acetone via the Claisen condensation method. Under alkaline conditions, a 1-(substituted phenyl)oxy-2,4-pentanedione compound is added to an aqueous solution containing calcium ions and / or zinc ions. After the reaction, the mixture is filtered, washed, and dried to obtain a salt of the 1-(substituted phenyl)oxy-2,4-pentanedione compound. The specific reaction route is as follows: ； Where n is 0 or 1.

5. Use of the 1-(substituted phenyl)oxy-2,4-pentanedione compound according to claim 1 or a salt of the 1-(substituted phenyl)oxy-2,4-pentanedione compound according to any one of claims 2 to 3 as a PVC stabilizer.

6. A PVC stabilizer composition, characterized in that The PVC stabilizer composition comprises at least one of the 1-(substituted phenyl)oxy-2,4-pentanedione compound according to claim 1 or the salt of the 1-(substituted phenyl)oxy-2,4-pentanedione compound according to any one of claims 2 to 3.

7. The PVC stabilizer composition according to claim 6, characterized in that The PVC stabilizer composition includes a mixture of 1-phenoxy-2,4-pentanedione and 1-(β-naphthyl)oxy-2,4-pentanedione calcium.

8. The PVC stabilizer composition according to claim 6, characterized in that The amount of the PVC stabilizer composition is 1%-5% of the total mass of PVC.

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