Stabilizer for odorless artificial leather and preparation method thereof

Abstract

The invention relates to a stabilizer for odorless artificial leather, a preparation method of the stabilizer, a coating laminating material composition for PVC artificial leather, a corresponding coating laminating material for the PVC artificial leather and the PVC artificial leather. The preparation method comprises the following steps: selecting an alpha-olefin dimer from a polyolefin coordination polymerization light component byproduct, designing and synthesizing a polyol ester stabilizer with a branched long carbon chain on the basis of the alpha-olefin dimer, and reacting with zinc acetate to introduce Zn < 2 + > to form a coordinate bond with hydroxyl to prepare the alpha-olefin dimer-polyol ester-zinc composite stabilizer. Wherein the alpha olefin dimer has a branched non-polar carbon chain structure and is used for reducing the degree of crystallinity of PVC, the alpha olefin dimer is matched with the isophthalate plasticizer for use, so that the low-temperature flexibility of the PVC composite resin can be improved, the alpha olefin dimer is used as a resin bonding agent for PVC artificial leather, the polyhydric alcohol part is chelated with Zn < 2 + > and is used for absorbing HCl released by PVC, and the stability of a PVC product is improved. Meanwhile, the molecular weight and boiling point of the polyol ester stabilizer are higher, and the polyol ester stabilizer has lower odor.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of PVC stabilizers, and particularly relates to a non-odor artificial leather stabilizer, a preparation method thereof, a PVC artificial leather coating and lamination material composition, and a corresponding PVC artificial leather coating and lamination material and PVC artificial leather. BACKGROUND

[0002] Polyvinyl chloride (PVC) is the main raw material in the production and development of artificial leather, and PVC artificial leather is a plastic product that looks and feels like leather and can replace it. It usually takes fabric as the base, coats a layer of resin lamination agent on the base, and then heats it to make it plasticized to obtain PVC artificial leather similar to natural leather, which has the advantages of softness and wear resistance, and is currently widely used in automotive interiors. The melting temperature of high-polymerization-degree PVC raw materials is very high, and the flowability of the melt is poor, making it difficult to process. At the same time, the molecular chain stability of PVC is insufficient, and it is prone to degradation under mechanical stress, oxygen, high temperature, light, and other conditions. The most important feature of PVC degradation is the removal of HCl to generate conjugated polyenes, which causes PVC to discolor. The removed HCl has a catalytic effect on further degradation of PVC. The poor thermal stability of PVC under stress, high temperature, and oxygen is the root cause of its degradation. In practical applications, an effective method to improve the stability of PVC products is to use stabilizers to absorb and neutralize the HCl released during PVC processing, thereby eliminating the catalytic degradation effect of hydrogen chloride.

[0003] In summary, in order to improve the flowability and stability of PVC, reduce the processing temperature, and make it easier to produce and process, it is necessary to add plasticizers and stabilizers to various PVC products. For the manufacturing process of PVC artificial leather, a viscous resin lamination agent is also used to bond the foaming layer and the PVC artificial leather base. This part of the additive or resin mixture is prone to volatilization or decomposition, producing small molecules that cause strong odor, affecting user experience.

[0004] The methods for improving odor include improving the stability of the additive, using water-based resin instead of solvent-based resin, and adding odor adsorbing materials. Among them, the measure of adding activated carbon and other odor adsorbing materials has high cost and limited effect. The current improvement for plasticizers is to use terephthalate instead of phthalate. There is no good method for the improvement of calcium stearate, zinc stearate, and other PVC stabilizers. The use of water-based resin can reduce the overall VOC emissions, but water-based resin usually uses ammonia, triethylamine, and other alkaline neutralizing agents to neutralize the carboxylic acid, which still has a pungent odor affecting the experience. SUMMARY

[0005] In view of the defects of the prior art, the technical problem to be solved by the present application is to design and synthesize a new polyol ester stabilizer, which has a plasticizing effect in addition to stabilizing PVC resin, and when used in combination with terephthalate plasticizers, the crystallinity of the PVC resin is reduced, so that the PVC artificial leather coating adhesive has better thermal stability, low-temperature flexibility, moderate peel strength and lower odor.

[0006] The present application is realized by the following technical solutions:

[0007] In a first aspect, a stabilizer has a general molecular structure as follows:

[0008] wherein R1 is a hydrocarbon group of 10 to 50 carbon atoms, the hydrocarbon group contains at least one branch, n is a positive integer greater than or equal to 1, R2 is selected from a hydrocarbon group or a hydrocarbon alcohol, and M is Zn.

[0009] Preferably, R1 is a hydrocarbon group of 10 to 40 carbon atoms; more preferably, R1 is a hydrocarbon group of 12 to 36 carbon atoms.

[0010] Preferably, R2 is selected from -CH2OH or -CH3.

[0011] In a second aspect, a preparation method of the stabilizer described above includes: performing an esterification reaction on an alpha olefin dimer anhydride and a polyol containing at least one primary hydroxyl group to obtain an alpha olefin dimer anhydride-polyol ester, and then performing a reaction on the alpha olefin dimer anhydride-polyol ester and zinc acetate to obtain the stabilizer.

[0012] A corresponding esterification reaction step is shown in the following schematic diagram:

[0013]

[0014] A schematic diagram of the reaction step of the esterification reaction product and zinc acetate is as follows:

[0015]

[0016] wherein a general structure of the polyol containing at least one primary hydroxyl group is as follows: wherein n is a positive integer greater than or equal to 1, and R2 is selected from a hydrocarbon group or a hydrocarbon alcohol.

[0017] Preferably, an esterification catalyst is used in the esterification reaction to accelerate the esterification reaction rate and shorten the reaction time.

[0018] Preferably, the esterification catalyst is selected from p-toluenesulfonic acid.

[0019] Preferably, the amount of the esterification catalyst is 0.1-1.0wt% of the total amount of the reactants.

[0020] The polyol containing at least one primary hydroxyl group is selected from one or more combinations of erythritol, sorbitol, xylitol, mannitol and rhamnitol.

[0021] The alpha olefin dimeric anhydride is selected from one or more combinations of C6-alpha olefin dimeric anhydride, C8-alpha olefin dimeric anhydride, C 10 -alpha olefin dimeric anhydride, C 12 -alpha olefin dimeric anhydride, C 14 -alpha olefin dimeric anhydride, C 16 -alpha olefin dimeric anhydride and C 18 -alpha olefin dimeric anhydride.

[0022] In a third aspect, the use of the stabilizer described above, the use of the stabilizer in the preparation of a coating compound for PVC artificial leather and PVC artificial leather.

[0023] In a fourth aspect, a coating compound for PVC artificial leather composition, comprising: the stabilizer described above, a PVC paste resin, an inorganic filler, a defoaming agent and a plasticizer.

[0024] The average polymerization degree of the PVC paste resin is not less than 1000.

[0025] Preferably, the PVC paste resin is selected from P-440 type PVC paste resin.

[0026] The inorganic filler is selected from one or more combinations of calcium carbonate, barium sulfate, talc powder, silicon powder, kaolin and silicon dioxide.

[0027] Preferably, the calcium carbonate is selected from heavy calcium carbonate, and the silicon dioxide is selected from fumed silicon dioxide.

[0028] The defoaming agent is selected from silicone defoaming agent, mineral oil defoaming agent or a combination of both.

[0029] The plasticizer is selected from terephthalate plasticizers, in which the number of alcohol side chain carbons is 8-16, preferably, the plasticizer is selected from dioctyl terephthalate (DOTP).

[0030] Preferably, the coating compound for PVC artificial leather composition further comprises epoxidized vegetable oil, and more preferably, the epoxidized vegetable oil is selected from epoxidized soybean oil.

[0031] Further, the coating compound for PVC artificial leather composition is prepared from the following raw materials in the following weight percentages: 100 parts of PVC paste resin, 5-15 parts of the stabilizer described above, 10-20 parts of inorganic filler, 40-60 parts of plasticizer and 0.1-1 parts of defoaming agent.

[0032] Further, the coating and laminating material composition for PVC artificial leather is prepared from the following raw materials in percentage by weight: 100 parts of PVC paste resin, 5-15 parts of the stabilizer described above, 10-20 parts of inorganic filler, 40-60 parts of plasticizer, 0.1-1 part of defoaming agent, and 1-10 parts of epoxidized vegetable oil.

[0033] In a fifth aspect, a method for preparing a coating and laminating material for PVC artificial leather comprises the following steps:

[0034] S1, adding PVC paste resin, the stabilizer described above, and inorganic filler into a grinder in proportion by weight, and grinding;

[0035] S2, adding defoaming agent into the material prepared in S1, and continuing to grind at room temperature to obtain a powdery mixture;

[0036] S3, adding the mixture prepared in S2 and plasticizer into a vacuum grinder and stirring machine in proportion by weight, and preparing a uniformly dispersed paste through vacuum grinding and stirring;

[0037] S4, filtering the paste prepared in S3 to obtain the coating and laminating material for PVC artificial leather.

[0038] Preferably, in step S1, epoxidized vegetable oil, PVC paste resin, stabilizer, and inorganic filler are added into a vertical dispersion grinder in proportion by weight.

[0039] Preferably, in step S1, the grinding temperature is controlled to be 75-85℃.

[0040] In a sixth aspect, a method for manufacturing PVC artificial leather comprises: coating the coating and laminating material for PVC artificial leather prepared in step S4 described above on a PVC artificial leather base, laminating with a roller, and drying at 150-200℃ to obtain PVC artificial leather.

[0041] In a seventh aspect, PVC artificial leather is manufactured by the manufacturing method described above.

[0042] The technical scheme of the present application has the following beneficial effects: a polyol ester stabilizer with a branched long carbon chain is designed and synthesized, wherein the best scheme is to select an alpha olefin dimer derived from light component byproducts of polyolefin coordination polymerization, to synthesize a corresponding polyol ester through anhydridization of the alpha olefin dimer and reaction of the anhydride with a polyol, and to introduce Zn 2+ and to form a coordination bond with hydroxyl groups to prepare an alpha olefin dimer-polyol ester-zinc composite stabilizer, wherein the alpha olefin dimer has a branched nonpolar carbon chain structure for reducing the crystallinity of PVC, and is used in combination with an isophthalate plasticizer to improve the low-temperature flexibility of PVC composite resin and as a resin laminating agent for PVC artificial leather. The polyol part of the stabilizer chelates Zn 2+For absorbing the HCl released by PVC, improving the stability of PVC products. At the same time, the molecular weight and boiling point of the polyol ester stabilizer are higher, and compared with the small molecule stabilizer on the market, it is more difficult to volatilize, so the odor is obviously lower. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 C6 dimer-1,2-dirhamnol ester, C6 dimer-1,2-dirhamnol ester-zinc and C 10 Infrared spectrum of dimer-1,2-dirhamnol ester-zinc. DETAILED DESCRIPTION

[0044] The application will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the application and not intended to limit the scope of the application. In addition, it should be understood that those skilled in the art can make various modifications or changes to the application after reading the content disclosed in the application, and these equivalent forms also fall within the scope defined by the claims attached hereto.

[0045] It should be noted that the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the exemplary embodiments according to the application. As used herein, the singular form is intended to include the plural form unless the context clearly indicates otherwise, and furthermore, it should be understood that when the terms "comprise" and / or "include" are used in the specification, they indicate the presence of a feature, step, operation, device, component and / or combination thereof.

[0046] If the specific conditions of the experiment are not specified in the examples, they are generally in accordance with the conventional conditions in the art, or in accordance with the conditions recommended by the reagent company; The materials, reagents, etc. used in the examples can be purchased through commercial channels if not otherwise specified.

[0047] The anhydride raw material used to prepare the stabilizer is from Yabene Technology, which is an α-olefin dimer anhydride with C6-C 10 The preparation method has been disclosed in Polymers, 2020, 12, 744 (DOI: 10.3390 / polym12040744), CN117866173A and other literatures, so it will not be repeated here.

[0048] Example 1

[0049] Into a reaction vessel, 33.23 g (0.2 mol) of rhamnitol (Jiangsu Aofu Bio) and 26.64 g (0.1 mol) of C6 dimer anhydride, 0.3 g of esterification catalyst p-toluenesulfonic acid were added, 70 mL of xylene was added to dissolve, and xylene was used as a water-carrying solvent, and the temperature was raised to 170°C under stirring for 3 hours. A water trap and a condenser were added to the reaction device to continuously remove and condense the water generated by the esterification reaction, and the water was collected in the water trap. After the reaction was completed, the temperature was lowered to 80°C, and the solvent xylene was recovered by distillation under reduced pressure. The remaining material in the container was C6 dimer-1,2-dirhamnitol ester. At the same time, the amount of water collected in the water trap was weighed and compared with the theoretical amount of water to calculate the yield of C6 dimer-1,2-dirhamnitol ester, which was 94.4%.

[0050] C6 dimer-1,2-dirhamnitol ester was added to 150 mL of anhydrous ethanol and 20.63 g (0.094 mol) of zinc acetate dihydrate, and the temperature was raised to 140°C for 3 hours. The evaporated ethanol-acetic acid mixed solvent was collected, and the content of acetic acid in the product C6 dimer-1,2-dirhamnitol ester-zinc was determined by acid-base titration to determine the yield of the product C6 dimer-1,2-dirhamnitol ester-zinc, which was 97.8%.

[0051] The structure of the final product C6 dimer-1,2-dirhamnitol ester-zinc was confirmed.

[0052] Nuclear magnetic hydrogen spectrum 1H NMR (400 MHz, CDC13): δ 0.80-0.94 (6H, 0.87 (dd, J = 6.63, 6.63 Hz), 0.87 (dd, J = 6.50, 6.50 Hz)), 1.09-1.56 (16H, 1.15 (d, J = 6.17 Hz), 1.15 (d, J = 6.17 Hz), 1.24 (dddd, J = 7.00, 7.00, 6.87, 6.87 Hz), 1.24 (dddd, J = 7.00, 7.00, 6.87, 6.87 Hz), 1.28 (ddq, J = 6.87, 6.87, 6.63 Hz), 1.28 (ddq, J = 6.87, 6.87, 6.63 Hz), 1.30 (ddq, J = 6.63, 6.63, 6.50 Hz), 1.30 (ddq, J = 6.63, 6.63, 6.50 Hz), 1.35 (dddd, J = 7.43, 7.43, 7.00, 7.00 Hz), 1.35 (dddd, J = 7.43, 7.43, 7.00, 7.00 Hz), 1.47 (dddd, J = 7.43, 7.43, 6.63, 6.63 Hz), 1.47 (dddd, J = 7.43, 7.43, 6.63, 6.63 Hz)), 1.82-2.08 (4H, 1.89 (dd, J = 7.43, 7.43 Hz), 1.89 (dd, J = 7.43, 7.43 Hz), 2.01 (ddd, J = 7.43, 7.43, 7.15 Hz), 2.01 (ddd, J = 7.43, 7.43, 7.15 Hz)), 2.12-2.24 (2H, 2.18 (d, J = 7.53 Hz), 2.18 (d, J = 7.53 Hz)), 2.84-3.05 (3H, 2.90 (d, J = 7.04 Hz), 2.90 (d, J = 7.04 Hz), 2.96 (dddd, J = 7.53, 7.53, 7.04, 7.04 Hz)), 3.62-3.93 (6H, 3.70 (qd, J = 6.17, 4.32 Hz), 3.70 (qd, J = 6.17, 4.31 Hz), 3.77 (dd, J = 4.32, 3.39 Hz), 3.77 (dd, J = 4.31, 3.40 Hz), 3.85 (dd, J = 3.40, 3.36 Hz), 3.87 (dd, J = 3.39, 3.35 Hz)), 3.95-4.09 (2H, 4.02 (ddd, J = 6.26, 6.26, 3.36 Hz), 4.02 (ddd, J = 6.26, 6.26, 3.35 Hz)), 4.53-4.65 (4H, 4.58 (d, J = 6.26 Hz), 4.58 (d, J = 6.26 Hz), 4.59 (d, J = 6.26 Hz), 4.59 (d, J = 6.26 Hz)), 5.30 (1H, dd, J = 7.15, 7.15 Hz), 5.30-5.35 (2H, br), 5.41-5.45 (2H, br).

[0053] NMR 13 C NMR (100 MHz, CDC13): δ 13.70 (1C, s), 14.05 (1C, s), 18.65-18.75 (2C, 18.70 (s), 18.70 (s)), 22.10 (1C, s), 22.50 (1C, s), 27.90 (1C, s), 28.50 (1C, s), 30.00 (1C, s), 31.20 (1C, s), 32.65 (1C, s), 36.40 (1C, s), 42.00 (1C, s), 43.00 (1C, s), 68.35-68.45 (2C, 68.40 (s), 68.40 (s)), 69.18-69.28 (2C, 69.23 (s), 69.23 (s)), 72.21-72.31 (2C, 72.26 (s), 72.26 (s)), 74.35-74.45 (2C, 74.40 (s), 74.40 (s)), 74.65-74.75 (2C, 74.70 (s), 74.70 (s)), 129.60 (1C, s), 140.05 (1C, s), 172.15 (1C, s), 176.18 (1C, s).

[0054] Example 2

[0055] 33.23 g (0.2 mol) of rhamnitol (Jiangsu Aofu Bio) and 37.86 g (0.1 mol) of C 10 The dimeric anhydride, 0.35 g of esterification catalyst p-toluenesulfonic acid, was added to the reaction container, 80 mL of dimethylbenzene was added to dissolve, and dimethylbenzene was used as a water-carrying solvent. The temperature was raised to 170°C under stirring for 3 hours. A water trap and a condenser tube were added to the reaction device to continuously carry out and condense the water generated by the esterification reaction, and the water was collected in the water trap. After the reaction was completed, the temperature was lowered to 80°C, and dimethylbenzene was recovered by distillation under reduced pressure. The remaining substance in the container was C 10 The dimeric anhydride, 0.35 g of esterification catalyst p-toluenesulfonic acid, was added to the reaction container, 80 mL of dimethylbenzene was added to dissolve, and dimethylbenzene was used as a water-carrying solvent. The temperature was raised to 170°C under stirring for 3 hours. A water trap and a condenser tube were added to the reaction device to continuously carry out and condense the water generated by the esterification reaction, and the water was collected in the water trap. After the reaction was completed, the temperature was lowered to 80°C, and dimethylbenzene was recovered by distillation under reduced pressure. The remaining substance in the container was C 10 The yield of the dimer-1,2-dirhamnitol ester was 92.3%.

[0056] C 10Dimer-1,2-dirhannol ester was added to 150 mL of absolute ethanol with 20.19 g (0.092 mol) of zinc acetate dihydrate, warmed to 140°C for 3 hours, and the evaporated ethanol-acetic acid mixture solvent was collected, and the content of acetic acid therein was determined by acid-base titration to determine the product C 10 The yield of dimer-1,2-dirhannol ester-zinc was 96.0%.

[0057] The final product C 10 The structure of dimer-1,2-dirhannol ester-zinc was confirmed:

[0058] NMR hydrogen spectrum 1H NMR (400 MHz, CDC13): δ 0.80-0.93 (6H, 0.87 (dd, J = 7.00, 7.00 Hz), 0.87 (dd, J = 7.00, 7.00 Hz)), 1.09-1.56 (32H, 1.15 (d, J = 6.17 Hz), 1.15 (d, J = 6.17 Hz), 1.23 (dddd, J = 6.50, 6.50, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.50, 6.50, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.63, 6.63, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.63, 6.63, 6.50, 6.50 Hz), 1.24 (dddd, J = 6.50, 6.50, 6.50, 6.50 Hz), 1.24 (dddd, J = 6.50, 6.50, 6.50, 6.50 Hz), 1.24 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.24 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.24 (dddd, J = 7.00, 7.00, 6.87, 6.87 Hz), 1.24 (dddd, J = 7.00, 7.00, 6.87, 6.87 Hz), 1.24 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.24 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.38 (dddd, J = 7.43, 7.43, 6.63, 6.63 Hz), 1.38 (dddd, J = 7.43, 7.43, 6.63, 6.63 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J =43, 6.87, 6.87 Hz)), 1.82-2.09 (4H, 1.89 (dd, J = 7.43, 7.43 Hz), 1.89 (dd, J = 7.43, 7.43 Hz), 2.01 (ddd, J = 7.43, 7.43, 7.15 Hz), 2.01 (ddd, J = 7.43, 7.43, 7.15 Hz)), 2.14-2.26 (2H, 2.20 (d, J = 7.53 Hz), 2.20 (d, J = 7.53 Hz)), 2.84-3.05 (3H, 2.90 (d, J = 7.03 Hz), 2.90 (d, J = 7.03 Hz), 2.96 (dddd, J = 7.53, 7.53, 7.03, 7.03 Hz)), 3.62-3.93 (6H, 3.70 (qd, J = 6.17, 4.32 Hz), 3.70 (qd, J = 6.17, 4.31 Hz), 3.77 (dd, J = 4.32, 3.39 Hz), 3.77 (dd, J = 4.31, 3.40 Hz), 3.85 (dd, J = 3.40, 3.36 Hz), 3.87 (dd, J = 3.39, 3.35 Hz)), 3.95-4.09 (2H, 4.02 (ddd, J = 6.26, 6.26, 3.36 Hz), 4.02 (ddd, J = 6.26, 6.26, 3.35 Hz)), 4.53-4.65 (4H, 4.58 (d, J = 6.26 Hz), 4.58 (d, J = 6.26 Hz), 4.59 (d, J = 6.26 Hz), 4.59 (d, J = 6.26 Hz)), 5.31 (1H, dd, J = 7.15, 7.15 Hz), 5.37-5.41 (2H, br), 5.45-5.50 (2H, br).

[0059] NMR Carbon Spectrum 13C NMR (100 MHz, CDC13): δ 14.00-14.10 (2C, 14.05 (s), 14.05 (s)), 18.65-18.75 (2C, 18.70 (s), 18.70 (s)), 22.60-22.70 (2C, 22.65 (s), 22.65 (s)), 25.00 (1C, s), 28.50 (1C, s), 29.20 (1C, s), 29.30-29.48 (5C, 29.35 (s), 29.40 (s), 29.40 (s), 29.40 (s), 29.43 (s)), 29.55-29.69 (2C, 29.60 (s), 29.64 (s)), 31.86-31.96 (2C, 31.91 (s), 31.91 (s)), 32.65 (1C, s), 36.40 (1C, s), 42.00 (1C, s), 43.00 (1C, s), 68.35-68.45 (2C, 68.40 (s), 68.40 (s)), 69.18-69.28 (2C, 69.23 (s), 69.23 (s)), 72.21-72.31 (2C, 72.26 (s), 72.26 (s)), 74.35-74.45 (2C, 74.40 (s), 74.40 (s)), 74.65-74.75 (2C, 74.70 (s), 74.70 (s)), 129.60 (1C, s), 140.05 (1C, s), 172.15 (1C, s), 176.18 (1C, s).

[0060] Example 3

[0061] The 36.43 g (0.2 mol) of mannitol (Macleod) was dissolved in 80 mL of xylene and added to a reaction vessel. After warming to 170°C with stirring, 32.25 g (0.1 mol) of C8 dimer anhydride and 0.35 g of esterification catalyst p-toluenesulfonic acid were added dropwise. The reaction was carried out at 180°C for 3 hours. A water trap and condenser were added to the reaction apparatus to continuously remove and condense the water produced by the esterification reaction. After the reaction was complete, the temperature was reduced to 80°C and the solvent xylene was recovered by distillation under reduced pressure. The remaining material in the vessel was C8 dimer-1,2-dimannitol ester. At the same time, the amount of water removed from the water trap was weighed and compared with the theoretical amount of water to calculate the yield of C8 dimer-1,2-dimannitol ester, which was 92.8%.

[0062] C8 dimer-1,2-dimannitol ester was added to 150 mL of anhydrous ethanol with 20.19 g (0.092 mol) of zinc acetate dihydrate, and the temperature was raised to 140°C for 3 hours. The evaporated ethanol-acetic acid mixed solvent was collected, and the content of acetic acid was determined by acid-base titration to determine the yield of the product C8 dimer-1,2-dimannitol ester-zinc as 98.4%.

[0063] The structure of the final product C8 dimer-1,2-dimannitol ester-zinc was confirmed:

[0064] 1H NMR (400 MHz, CDC13): δ 0.80-0.93 (6H, 0.87 (dd, J = 7.00, 7.00 Hz), 0.87 (dd, J = 7.00, 7.00 Hz)), 1.15-1.57 (18H, 1.23 (dddd, J = 6.63, 6.63, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.63, 6.63, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.24 (dddd, J = 7.00, 7.00, 6.50, 6.50 Hz), 1.24 (dddd, J = 7.00, 7.00, 6.50, 6.50 Hz), 1.24 (dddd, J = 7.00, 6.87, 6.87, 6.87 Hz), 1.24 (dddd, J = 7.00, 6.87, 6.87, 6.87 Hz), 1.24 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.24 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 6.87, 6.87 Hz), 1.28 (qdd, J = 7.00, 6.87, 6.87 Hz), 1.38 (dddd, J = 7.43, 7.43, 6.63, 6.63 Hz), 1.38 (dddd, J = 7.43, 7.43, 6.63, 6.63 Hz), 1.48 (dddd, J = 7.43, 7.43, 7.00, 7.00 Hz), 1.48 (dddd, J = 7.43, 7.43, 7.00, 7.00 Hz)), 1.82-2.09 (4H, 1.89 (dd, J = 7.43, 7.43 Hz), 1.89 (dd, J = 7.43, 7.43 Hz), 2.01 (ddd, J = 7.43, 7.43, 7.15 Hz), 2.01 (ddd, J = 7.43, 7.43, 7.15 Hz)), 2.12-2.24 (2H, 2.18 (d, J = 7.53 Hz), 2.18 (d, J = 7.53 Hz)), 2.84-3.05 (3H, 2.90 (d, J = 7.03 Hz), 2.90 (d, J = 7.03 Hz), 2.96 (dddd, J = 7.53, 7.53, 7.03, 7.03 Hz)), 3.45-3.56 (4H, 3.51 (d, J = 5.38 Hz), 3.51 (d, J = 5.38 Hz), 3.51 (d, J = 5.38 Hz), 3.51 (d, J = 5.38 Hz)), 3.79-4.09 (8H, 3.85 (dd, J = 3.46, 3.42 Hz), 3.85 (dd, J = 3.47, 3.43 Hz), 3.87 (dd, J = 3.42, 3.36 Hz), 3.87 (dd, J = 3.43, 3.36 Hz), 3.90 (ddd, J = 5.38, 5.38, 3.47 Hz), 3.90 (ddd, J = 5.38, 5.38, 3.46 Hz), 4.02 (ddd, J = 6.26, 6.26, 3.36 Hz), 4.02 (ddd, J = 6.26, 6.26, 3.36 Hz)), 4.52-4.65 (4H, 4.58 (d, J = 6.26 Hz), 4.58 (d, J = 6.26 Hz), 4.59 (d, J = 6.26 Hz), 4.59 (d, J = 6.26 Hz)), 5.31 (1H, dd, J = 7.15, 7.15 Hz), 5.38-5.42 (4H, br), 5.46-5.51 (2H, br).

[0065] NMR 13 C NMR (100 MHz, CDC13): δ 14.00-14.10 (2C, 14.05 (s), 14.05 (s)), 22.60-22.70 (2C, 22.65 (s), 22.65 (s)), 25.00 (1C, s), 28.50 (1C, s), 28.90 (1C, s), 29.30-29.45 (3C, 29.35 (s), 29.40 (s), 29.40 (s)), 31.31 (1C, s), 31.91 (1C, s), 32.65 (1C, s), 36.40 (1C, s), 42.00 (1C, s), 43.00 (1C, s), 65.40-65.50 (2C, 65.45 (s), 65.45 (s)), 69.18-69.28 (2C, 69.23 (s), 69.23 (s)), 72.21-72.31 (2C, 72.26 (s), 72.26 (s)), 73.55-73.65 (2C, 73.60 (s), 73.60 (s)), 74.35-74.45 (2C, 74.40 (s), 74.40 (s)), 75.25-75.35 (2C, 75.30 (s), 75.30 (s)), 129.60 (1C, s), 140.05 (1C, s), 172.15 (1C, s), 176.18 (1C, s).

[0066] Example 4

[0067] Dissolve 36.43 g (0.2 mol) of mannitol (Mcln) in 100 mL of xylene added to a reaction vessel, and after warming to 170°C with stirring, add dropwise 37.86 g (0.1 mol) of C 10 Dimeric anhydride and 0.35 g of esterification catalyst p-toluenesulfonic acid are reacted at 180°C for 3 hours, a water trap and condenser are added to the reaction apparatus to continuously remove and condense water produced by the esterification reaction, and collect in the water trap. After the reaction is complete, the temperature is lowered to 80°C, and the solvent xylene is recovered by distillation under reduced pressure, and the remaining material in the vessel is C 10 Dimer-1,2-dimannitol ester. At the same time, the amount of water removed from the water trap is weighed, and compared with the theoretical amount of water removed to calculate C 10 The yield of dimer-1,2-dimannitol ester is 95.0%.

[0068] Dissolve 36.43 g (0.2 mol) of mannitol (Mcln) in 100 mL of xylene added to a reaction vessel, and after warming to 170°C with stirring, add dropwise 37.86 g (0.1 mol) of C 10 Dimer-1,2-dimannitol ester is added to 150 mL of anhydrous ethanol and 20.85 g (0.095 mol) of zinc acetate dihydrate, and reacted at 140°C for 3 hours, and the ethanol-acetic acid mixed solvent evaporated is collected, and the content of acetic acid therein is determined by acid-base titration to determine the product C 10 The yield of dimer-1,2-dimannitol ester-zinc is 96.5%.

[0069] The final product C 10 Confirmation of the structure of dimer-1,2-dimannitol ester-zinc:

[0070] 1H NMR (400 MHz, CDC13): δ 0.80-0.93 (6H, 0.87 (dd, J = 7.00, 7.00 Hz), 0.87 (dd, J = 7.00, 7.00 Hz)), 1.14-1.56 (26H, 1.23 (dddd, J = 6.50, 6.50, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.50, 6.50, 6.50, 6.50 Hz), 1.23 (dddd, J = 7.00, 7.00, 6.87, 6.87 Hz), 1.23 (dddd, J = 7.00, 7.00, 6.87, 6.87 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.63, 6.63, 6.50, 6.50 Hz), 1.23 (dddd, J = 6.63, 6.63, 6.50, 6.50 Hz), 1.24 (dddd, J = 6.50, 6.50, 6.50, 6.50 Hz), 1.24 (dddd, J = 6.50, 6.50, 6.50, 6.50 Hz), 1.24 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.24 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.24 (dddd, J = 7.00, 7.00, 6.87, 6.87 Hz), 1.24 (dddd, J = 7.00, 7.00, 6.87, 6.87 Hz), 1.24 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.24 (dddd, J = 6.87, 6.87, 6.50, 6.50 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.38 (dddd, J = 7.43, 7.43, 6.63, 6.63 Hz), 1.38 (dddd, J = 7.43, 7.43, 6.63, 6.63 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz), 1.48 (dddd, J = 7.43, 7.43, 6.87, 6.87 Hz)), 1.82-2.09 (4H, 1.89 (dd, J = 7.43, 7.43 Hz), 1.89 (dd, J = 7.43, 7.43 Hz), 2.01 (ddd, J = 7.43, 7.43, 7.15 Hz), 2.01 (ddd, J = 7.43, 7.43, 7.15 Hz)), 2.14-2.26 (2H, 2.20 (d, J = 7.53 Hz), 2.20 (d, J = 7.53 Hz)), 2.84-3.05 (3H, 2.90 (d, J = 7.03 Hz), 2.90 (d, J = 7.03 Hz), 2.96 (dddd, J = 7.53, 7.53, 7.03, 7.03 Hz)), 3.45-3.56 (4H, 3.51 (d, J = 5.38 Hz), 3.51 (d, J = 5.38 Hz), 3.51 (d, J = 5.38 Hz), 3.51 (d, J = 5.38 Hz)), 3.79-4.09 (8H, 3.85 (dd, J = 3.46, 3.42 Hz), 3.85 (dd, J = 3.47, 3.43 Hz), 3.87 (dd, J = 3.42, 3.36 Hz), 3.87 (dd, J = 3.43, 3.36 Hz), 3.90 (ddd, J = 5.38, 5.38, 3.47 Hz), 3.90 (ddd, J = 5.38, 5.38, 3.46 Hz), 4.02 (ddd, J = 6.26, 6.26, 3.36 Hz), 4.02 (ddd, J = 6.26, 6.26, 3.36 Hz)), 4.52-4.65 (4H, 4.58 (d, J = 6.26 Hz), 4.58 (d, J = 6.26 Hz), 4.59 (d, J = 6.26 Hz), 4.59 (d, J = 6.26 Hz)), 5.31 (1H, dd, J = 7.15, 7.15 Hz), 5.40-5.45 (4H, br).

[0071] 5.48-5.55 (2H, br).

[0072] NMR Carbon Spectrum 13C NMR (100 MHz, CDC13): δ 14.00-14.10 (2C, 14.05 (s), 14.05 (s)), 22.60-22.70 (2C, 22.65 (s), 22.65 (s)), 25.00 (1C, s), 28.50 (1C, s), 29.20 (1C, s), 29.30-29.48 (5C, 29.35 (s), 29.40 (s), 29.40 (s), 29.40 (s), 29.43 (s)), 29.55-29.69 (2C, 29.60 (s), 29.64 (s)), 31.86-31.96 (2C, 31.91 (s), 31.91 (s)), 32.65 (1C, s), 36.40 (1C, s), 42.00 (1C, s), 43.00 (1C, s), 65.40-65.50 (2C, 65.45 (s), 65.45 (s)), 69.18-69.28 (2C, 69.23 (s), 69.23 (s)), 72.21-72.31 (2C, 72.26 (s), 72.26 (s)), 73.55-73.65 (2C, 73.60 (s), 73.60 (s)), 74.35-74.45 (2C, 74.40 (s), 74.40 (s)), 75.25-75.35 (2C, 75.30 (s), 75.30 (s)), 129.60 (1C, s), 140.05 (1C, s), 172.15 (1C, s), 176.18 (1C, s).

[0073] Example 5

[0074] The coating and lamination composition for PVC artificial leather was prepared with 100 parts of PVC paste resin, and the following raw materials in weight percentage: C6 dimer anhydride-1,2-dirhamnol ester-zinc prepared in Example 1 7 parts, heavy calcium carbonate 6 parts, fumed silica 6 parts, defoaming agent 0.4 parts, dioctyl terephthalate (DOTP) 48 parts.

[0075] Example 6

[0076] The coating and lamination composition for PVC artificial leather was prepared with 100 parts of PVC paste resin, and the following raw materials in weight percentage: C 10 dimer anhydride-1,2-dirhamnol ester-zinc prepared in Example 2 7 parts, heavy calcium carbonate 6 parts, fumed silica 6 parts, defoaming agent 0.4 parts, dioctyl terephthalate (DOTP) 48 parts.

[0077] Example 7

[0078] A coating and lamination composition for PVC artificial leather was formulated with 100 parts of PVC paste resin and prepared from the following raw materials in the weight percentage: C8 dimer anhydride-1,2-dimannitol ester-zinc prepared in Example 3 7 parts, heavy calcium carbonate 6 parts, fumed silica 6 parts, defoaming agent 0.4 parts, dioctyl terephthalate (DOTP) 48 parts.

[0079] Example 8

[0080] A coating and lamination composition for PVC artificial leather was formulated with 100 parts of PVC paste resin and prepared from the following raw materials in the weight percentage: C8 dimer anhydride-1,2-dimannitol ester-zinc prepared in Example 4 8 parts, heavy calcium carbonate 6 parts, fumed silica 6 parts, defoaming agent 0.4 parts, dioctyl terephthalate (DOTP) 48 parts. 10

[0081] Example 9

[0082] A coating and lamination composition for PVC artificial leather was formulated with 100 parts of PVC paste resin and prepared from the following raw materials in the weight percentage: C8 dimer anhydride-1,2-dimannitol ester-zinc prepared in Example 2 7 parts, heavy calcium carbonate 6 parts, fumed silica 6 parts, defoaming agent 0.4 parts, dioctyl terephthalate (DOTP) 48 parts. 10

[0083] Example 10

[0084] A coating and lamination composition for PVC artificial leather was formulated with 100 parts of PVC paste resin and prepared from the following raw materials in the weight percentage: C8 dimer anhydride-1,2-dimannitol ester-zinc prepared in Example 4 8 parts, heavy calcium carbonate 6 parts, fumed silica 6 parts, defoaming agent 0.4 parts, dioctyl terephthalate (DOTP) 48 parts. 10

[0085] Comparative Example 1

[0086] A coating and lamination composition for PVC artificial leather was formulated with 100 parts of PVC paste resin and prepared from the following raw materials in the weight percentage: commercially available calcium-zinc carboxylate composite stabilizer CZ-106-2 (Shanghai Changfeng) 8 parts, epoxidized soybean oil 2 parts, heavy calcium carbonate 6 parts, fumed silica 6 parts, defoaming agent 0.4 parts, dioctyl terephthalate (DOTP) 48 parts.

[0087] The method of manufacturing the lamination composition of Examples 5-10 and Comparative Example 1 includes the following steps:

[0088] ​​​S1, P-440 type PVC paste resin (Zhongtai Chemical, average polymerization degree 1500), stabilizer, epoxidized soybean oil and inorganic filler were added into a vertical dispersion grinder according to the material ratio, the grinding temperature was controlled at 75-85°C, and after grinding for 60 min with the dispersion disc opened, it was cooled to room temperature;

[0089] S2, silicone defoaming agent was added to the material prepared in S1, and the room temperature grinding was continued for 20 min to prepare a powdery mixture;

[0090] S3, the powdery mixture prepared in S2 and plasticizer dioctyl terephthalate were added into a vacuum grinding stirrer according to the formula ratio, and a uniformly dispersed paste was prepared after vacuum grinding and stirring for 30 min;

[0091] S4, the paste prepared in S3 was filtered with a 200 mesh screen to obtain a PVC artificial leather coating and lamination material.

[0092] On the basis of S1-S4, PVC artificial leather was manufactured through step S5.

[0093] S5, the PVC artificial leather coating and lamination material prepared in S4 was uniformly coated on the PVC artificial leather base at a coating amount of 80 g per yard, and then the fabric cloth was laminated with a roller, and then dried at 175°C to obtain the PVC artificial leather.

[0094] Test section

[0095] Infrared spectrum analysis: the intermediate product C6 dimer-1,2-dirhamnol ester prepared in Example 1 and the final products C6 dimer-1,2-dirhamnol ester-zinc, C6 dimer-1,2-dirhamnol ester-zinc of Example 1, Example 2 were characterized by using Nicolet 5700 Fourier transform infrared spectrum. 0.1 g of the corresponding sample to be tested was completely mixed with dry KBr, and the sample was prepared by pressing at 20 Mpa for 1 min, and then the infrared spectrum test was carried out, and the test results are shown in 10 The dimer-1,2-dirhamnol ester-zinc was characterized in the range of 400-4000 cm -1 -1. The corresponding sample to be tested was weighed 0.1 g and completely mixed with dry KBr, and the sample was prepared by pressing at 20 Mpa for 1 min, and then the infrared spectrum test was carried out, and the test results are shown in Figure 1

[0096] Thermal stability test of PVC artificial leather coating and lamination material: including the dynamic and static thermal stability of the lamination material, wherein the static thermal stability test refers to the standard GB / T 2917.1-2002, and the static thermal stability of the lamination material is tested by using Congo red method, and the test temperature is set at 200±1°C;

[0097] ​The dynamic thermal stability of the coating material was tested by using the conductance method, i.e. the HCl produced by degradation of the PVC artificial leather was absorbed by deionized water, and the degree of degradation of the PVC was investigated by measuring the change of the conductance of the water solution with time during the whole thermal degradation process. The artificial leather used for testing had a size of 2x2x1 mm, the testing temperature was 180±1℃, and the time corresponding to the conductance of the water solution reaching 50 μS·cm -1 was taken as the dynamic thermal stability time.

[0098] Peeling strength test of the coating material for PVC artificial leather: a tensile testing machine was used to test the peeling strength at a tensile strength of 100 mm / min, and the size of the coating material film used for testing was 30x200x1 mm.

[0099] Low temperature flexibility test of the coating material for PVC artificial leather: a horizontal low temperature cold resistance testing machine was used, and the low temperature was set to 0 to -30℃, and the brittle folding of the coating material film at low temperature was tested.

[0100] Odor test of the PVC artificial leather: the test standard of PV-3900-2000-odor test of parts in the interior of automobiles was referred to, and the odor of the PVC artificial leather was divided into 1-6 grades, and the meaning of each grade was listed as follows:

[0101] 1st grade: no odor;

[0102] 2nd grade: odor, but no disturbing odor;

[0103] 3rd grade: obvious odor, but no disturbing odor;

[0104] 4th grade: disturbing odor;

[0105] 5th grade: strong disturbing odor;

[0106] 6th grade: unbearable odor.

[0107] The PVC artificial leathers prepared in Examples 5-10 and Comparative Example 1 were tested according to the grades.

[0108] The above test results are listed in Table 1.

[0109] The test results of the infrared spectrum of Figure 1 showed that the absorption bands at 3300 cm -1 and 2950 cm -1 indicated the stretching vibration of the hydroxyl (-O-H) group and the -C-H group in the hydrocarbon group from the sample, respectively, and the absorption peak near 1730 cm -1 could be attributed to the ester carbonyl bond of the sample.

[0110] For the final product C6 dimer-1,2-rhamnitol ester-zinc of Example 1, 2, 10 The absorption peaks of dimer-1,2-rhamnitol ester-zinc near 3300 cm -1 and 1730 cm -1 are all shifted to high wave number, because both ester carbonyl and alcohol hydroxyl form coordinate bond with Zn 2+ , and the electron withdrawing effect of Zn leads to the decrease of polarity of carbonyl and hydroxyl, thus the infrared absorption peaks are shifted to high wave number. For the intermediate product C6 dimer-1,2-rhamnitol ester, no zinc element is added, there is no obvious absorption peak between 1600-1650 cm -1 , 1440-1480 cm -1 and 600-700 cm -1 wave number, while C6 dimer-1,2-rhamnitol ester-zinc, C 10 dimer-1,2-rhamnitol ester-zinc has absorption peaks between 1600-1650 cm -1 , 1440-1480 cm -1 and 600-700 cm -1 wave number, which is attributed to the formation of C-O→Zn and C=O→Zn coordinate bond between Zn 2+ and the hydroxyl of polyol ester after adding zinc acetate.

[0111] Table 1

[0112]

[0113] It is found from the test results recorded in Table 1 that the polyol ester stabilizers based on α-olefin dimer anhydride prepared in Examples 1-4 have better thermal stability effect, especially in dynamic thermal stability effect, and the thermal stability of the laminates prepared in accordance with Examples 5-10 is better than that of the laminates prepared by using the commercially available stabilizers.

[0114] For the peeling strength test, the laminates prepared in Examples 5-10 and the commercially available stabilizers are close, and the C8 dimer anhydride-1,2-mannitol ester-zinc prepared by using dimannitol as raw material in Examples 3, 4 and C 10 dimer anhydride-1,2-mannitol ester-zinc as stabilizer has higher peeling strength, because it has higher hydroxyl content, and high content of polar groups is beneficial to the improvement of peeling strength.

[0115] For low temperature flexibility, the prepared coating materials of examples 5-10 are obviously higher than the coating materials prepared by the commercial stabilizers, because the commercial stabilizers are stearic acid and zinc / calcium salt complex samples, and the stearic acid only has a single long carbon chain, while the polyol ester stabilizers prepared by examples 1-4 are based on α-olefin dimer anhydride, and the non-polar branched carbon chain structure of oligomer α-olefin is introduced into the molecular chain of the stabilizers, and the branched structure has a stronger damage effect on the crystallinity of PVC, so as to improve the low temperature flexibility of the coating materials, and is beneficial to the coating materials for PVC artificial leather and the use of PVC artificial leather in extremely low temperature.

[0116] For the odor of PVC artificial leather, the use of stabilizers with higher molecular weight can effectively control the odor level, and the odor of the prepared PVC artificial leather by the coating materials of examples 5-10 can be controlled within 1-2 levels, which has a better effect compared with the commercial thermal stability.

[0117] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A stabilizer, characterized in that, The general molecular formula of stabilizers is: Wherein, R1 is a hydrocarbon group with 10 to 50 carbon atoms, the hydrocarbon group contains at least one branch, n is a positive integer greater than or equal to 1, R2 is selected from hydrocarbon groups or hydrocarbon alcohols, and M is Zn.

2. The method for preparing the stabilizer as described in claim 1, comprising: An α-olefin dimer anhydride is esterified with a polyol containing at least one primary hydroxyl group to obtain an α-olefin dimer anhydride-polyol ester, which is then reacted with zinc acetate to obtain a stabilizer. The general structural formula of polyols containing at least one primary hydroxyl group is: Where n is a positive integer greater than or equal to 1, and R2 is selected from hydrocarbon groups or hydrocarbon alcohols; The polyol containing at least one primary hydroxyl group is selected from one or more combinations of erythritol, sorbitol, xylitol, mannitol and rhamnitol; The α-olefin dimer anhydride is selected from: C6-α-olefin dimer anhydride, C8-α-olefin dimer anhydride, C... 10 -α-olefin dimer anhydride, C 12 -α-olefin dimer anhydride, C 14 -α-olefin dimer anhydride, C 16 -α-olefin dimer anhydrides and C 18 One or more combinations of -α-olefin dimer anhydrides.

3. The preparation method according to claim 2, characterized in that, The esterification reaction uses an esterification catalyst; Preferably, the esterification catalyst is selected from p-toluenesulfonic acid; Preferably, the amount of the esterification catalyst is 0.1-1.0 wt% of the total reactants.

4. The application of the stabilizer as described in claim 1, the application of the stabilizer in the manufacture of coating adhesives for PVC artificial leather and in PVC artificial leather.

5. A coating and laminating composition for PVC artificial leather, comprising: The stabilizer, PVC paste resin, inorganic filler, defoamer, and plasticizer as described in claim 1; Wherein, the average degree of polymerization of the PVC paste resin is not less than 1000; The inorganic filler is selected from one or more combinations of calcium carbonate, barium sulfate, talc, silica powder, kaolin, and silicon dioxide; The defoamer is selected from silicone defoamers, mineral oil defoamers, or a combination of both; The plasticizer is selected from terephthalate plasticizers, wherein the alcohol side chain has 8-16 carbon atoms.

6. The coating and bonding composition for PVC artificial leather according to claim 5, characterized in that, The coating and laminating composition for PVC artificial leather also includes epoxidized vegetable oil.

7. The coating and bonding composition for PVC artificial leather according to claim 5, characterized in that, The PVC artificial leather coating and bonding material composition is prepared from the following raw materials in weight percentage: 100 parts of PVC paste resin, 5-15 parts of the stabilizer as described in claim 1, 10-20 parts of inorganic filler, 40-60 parts of plasticizer, and 0.1-1 parts of defoamer. And / or, the PVC artificial leather coating and bonding composition is prepared from the following raw materials in weight percentages: 100 parts PVC paste resin, 5-15 parts of the stabilizer as described in claim 1, 10-20 parts inorganic filler, 40-60 parts plasticizer, 0.1-1 parts defoamer, and 1-10 parts epoxidized vegetable oil.

8. A method for preparing a coating and bonding material for PVC artificial leather, characterized in that, The preparation method includes the following steps: S1. PVC paste resin, the stabilizer described in claim 1, and inorganic filler are added to a grinding mill according to the material ratio and then ground. S2. Add defoamer to the material obtained in S1 and continue grinding at room temperature to obtain a powder mixture; S3. Add the mixture obtained in S2 and the plasticizer to a vacuum grinding mixer according to the formula ratio, and obtain a uniformly dispersed paste by vacuum grinding and mixing. S4. Filter the paste obtained in S3 to obtain the PVC artificial leather coating and bonding material.

9. A method for manufacturing PVC artificial leather, characterized in that, include: The PVC artificial leather obtained in step S4 of claim 8 is coated onto the PVC artificial leather base, and then dried at 150-200°C after being bonded with rollers to obtain PVC artificial leather.

10. A type of PVC artificial leather, characterized in that, It is manufactured by the manufacturing method described in claim 9.

Images