Super-branched high-performance environmentally friendly phthalate plasticizer, PVC product and preparation method and application thereof

Abstract

The application discloses a kind of super branched chain high-performance environmentally friendly phthalate plasticizers, PVC product and its preparation method and application, belong to material technical field.The super branched chain high-performance environmentally friendly phthalate plasticizers are esterified and polycondensed by polybasic acid and mixed dihydric alcohol in the presence of catalyst, and are obtained by monohydric alcohol end-capping;Polybasic acid includes trimellitic anhydride, mixed dihydric alcohol includes at least two of methyl propylene glycol, neopentyl glycol, ethylene glycol and propylene glycol.The super branched chain high-performance environmentally friendly phthalate plasticizers are well compatible with PVC, good color, with good viscosity, density, acid value and other performance indicators, which is used in PVC product, can make PVC product not only has superior aging resistance and electrical insulation performance, but also has outstanding oil extraction resistance, migration resistance, volatile resistance and thermal stability performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of materials, in particular to a kind of super-branch chain high-performance environmentally friendly phthalate plasticizer, PVC product and its preparation method and application. BACKGROUND

[0002] Plasticizer is a kind of "solvent-like" substance, added to plastic, resin or elastomer, etc. Material, enhance the flowability of plastic forming processing, can change the processability of material, increase plasticity, flexibility, tensile property or swelling, make plastic products have flexibility, a kind of organic substance, with high boiling point, difficult to volatilize, generally do not react with plastic. Mainly used in: acrylic, nitrile rubber products; PVC cable; Oil-resistant hose; Children's toys, artificial leather; Beverage hose, film, adhesive; Food packaging film; Medical hose, infusion bag and other fields.

[0003] However, with the problem of a small amount of volatilization, migration, extraction of plasticizer in the product, further cause environmental pollution, harm human health, product performance decreases with the loss of plasticizer and other problems.

[0004] In recent years, with the enhancement of global environmental awareness and the increasing perfection of environmental protection regulations, plasticizers develop towards high efficiency, high performance, low toxicity and other environmental protection directions, and the development of super-branch chain high-performance environmentally friendly polyester plasticizer with aging resistance, extraction resistance, migration resistance, difficult to volatilize and wide application has excellent market prospect.

[0005] Therefore, the present application is proposed. SUMMARY

[0006] One of the purposes of the present application is to provide a kind of super-branch chain high-performance environmentally friendly phthalate plasticizer, the super-branch chain high-performance environmentally friendly phthalate plasticizer is good in PVC compatibility, color is good, has good processing viscosity, specific gravity, acid value and other performance indicators, does not contain environmental control material such as o-benzene or DOA, meets the control requirements of various environmental protection regulations.

[0007] The second purpose of the present application is to provide a kind of preparation method of the above-mentioned super-branch chain high-performance environmentally friendly phthalate plasticizer, which is simple and easy to operate.

[0008] The third purpose of the present application is to provide a kind of PVC product containing the above-mentioned super-branch chain high-performance environmentally friendly phthalate plasticizer, due to its special super-branch chain network structure, by crosslinking grafting high molecular material into heterostructure with PVC, it has good compatibility in PVC product, and has good coupling coordination with other additives, so that the product has excellent aging resistance, migration resistance, extraction resistance, difficult to volatilize, durability and other application performance.

[0009] The fourth object of the present application is to provide a preparation method of the PVC product.

[0010] The fifth object of the present application is to provide an application of the PVC product.

[0011] The present application can be implemented as follows:

[0012] In the first aspect, the present application provides a hyperbranched chain high-performance environmentally friendly phthalate plasticizer, which is obtained by esterification and polycondensation of a polybasic acid and mixed diols in the presence of a catalyst, and terminated by a monohydric alcohol.

[0013] The polybasic acid includes trimellitic anhydride, and the mixed diols include at least two of methylpropanediol, neopentyl glycol, ethylene glycol, and propylene glycol.

[0014] In an optional embodiment, the mixed diols have at least one of the following characteristics:

[0015] Characteristic one: the mixed diols include ethylene glycol and neopentyl glycol;

[0016] Characteristic two: the molar ratio of the mixed diols to the polybasic acid is 0.85-1.5:2;

[0017] Characteristic three: the amounts of the diols in the mixed diols are equal.

[0018] In an optional embodiment, the catalyst has at least one of the following characteristics:

[0019] Characteristic one: the catalyst includes titanium tetraisopropoxide;

[0020] Characteristic two: the catalyst is added in an amount of 0.05-0.30wt% of the polybasic acid, preferably 0.15-0.2wt%.

[0021] In an optional embodiment, the monohydric alcohol has at least one of the following characteristics:

[0022] Characteristic one: the monohydric alcohol includes at least one of isooctanol, isononyl alcohol, and isodecyl alcohol;

[0023] Characteristic two: the monohydric alcohol is used in an amount of 150-200wt% of the polybasic acid.

[0024] In the second aspect, the present application provides a preparation method of the hyperbranched chain high-performance environmentally friendly phthalate plasticizer according to any one of the preceding embodiments, which includes the following steps: esterification and polycondensation of the polybasic acid and the mixed diols in the presence of the catalyst, and termination by the monohydric alcohol.

[0025] In an optional embodiment, the reaction process includes at least one of the following characteristics:

[0026] Feature one: the reaction comprises a temperature rising stage, an atmospheric pressure reaction stage and a negative pressure reaction stage in sequence, wherein the temperature after rising in the temperature rising stage is 180-200 DEG C, the temperature in the atmospheric pressure reaction stage is 215-220 DEG C, and when the acid value of the reaction system reaches 15-20 during the atmospheric pressure reaction, the negative pressure reaction is carried out under vacuum condition;

[0027] Feature two: the reaction process is carried out under the condition of protective atmosphere except the negative pressure reaction stage;

[0028] Feature three: after the negative pressure reaction, the temperature is lowered to 70-80 DEG C, and then purification treatment is carried out;

[0029] Feature four: the reaction system used in the reaction process comprises a reactor, a packed column, a condenser, an alcohol-water separation tank, a filter and a storage tank; the reactor is provided with a first inlet, a second inlet, a third inlet, a first outlet and a second outlet, the first inlet is used for introducing polybasic acid, dibasic alcohol and monohydric alcohol, the second inlet is used for introducing protective gas or vacuum, the third inlet and the first outlet are connected with the packed column, the second outlet is connected with the filter, the filter is further connected with the storage tank, the packed column is further connected with the condenser, the condenser is further connected with the alcohol-water separation tank, and the outlet of the alcohol-water separation tank is further connected with the top of the packed column;

[0030] Feature five: during the temperature rising process, the temperature of the distillation head of the packed column is controlled to be 90-110 DEG C to discharge the water generated in the reaction system.

[0031] In a third aspect, the application provides a PVC product containing the hyperbranched chain high-performance environmentally-friendly phthalate plasticizer according to any one of the preceding embodiments.

[0032] In optional embodiments, the PVC product further contains PVC material and auxiliary agents; the auxiliary agents include at least one of stabilizers, fillers, lubricants and antioxidants.

[0033] In optional embodiments, the PVC product has at least one of the following features:

[0034] Feature one: the type of the PVC material includes at least one of S-70 and S-65;

[0035] Feature two: the stabilizer includes calcium-zinc stabilizer;

[0036] Feature three: the filler includes calcium carbonate;

[0037] Feature four: the lubricant includes PE wax;

[0038] Feature five: the antioxidant includes antioxidant 1010;

[0039] Feature six: the PVC product includes 100 parts of PVC material, 60-70 parts of the super-branched chain high-performance environmentally friendly phthalate plasticizer, 3-7 parts of stabilizer, 50-60 parts of filler, 0.3-0.8 parts of lubricant, and 0.2-0.7 parts of antioxidant, in terms of mass fraction.

[0040] In a fourth aspect, the present application provides a method for preparing the PVC product according to any of the preceding embodiments, comprising the following steps: mixing the raw materials, tabletting, and tabletting.

[0041] In an optional embodiment, the mixing is plasticizing at 160-170°C for 3-5 minutes.

[0042] In an optional embodiment, the tabletting is performed at 180-190°C and a flat plate vulcanizing machine pressure of 45-55 tons for 30 seconds-5 minutes.

[0043] In a fifth aspect, the present application provides the use of the PVC product according to any of the preceding embodiments, for example, in the preparation of electric wires and cables, electrical tapes, gas pipes, rubberized cloth, leather, and rubber pads for motor vehicles, films, beverage hoses, dairy machinery rubber pads, or bottle cap rubber pads.

[0044] The beneficial effects of the present application include:

[0045] The super-branched chain high-performance environmentally friendly phthalate plasticizer prepared by using the specific raw materials in the present application has good compatibility with PVC, good color, and good performance indicators such as viscosity, density, and acid value, does not contain environmental control substances such as o-phenyl or DOA, and meets the requirements of various environmental regulations and controls; when used in PVC products, the PVC products not only have superior aging resistance and electrical insulation properties, but also have better oil extraction resistance, migration resistance, volatility resistance, and thermal stability. BRIEF DESCRIPTION OF DRAWINGS

[0046] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be considered as limiting the scope. For those skilled in the art, other related drawings can also be obtained without creative labor.

[0047] Figure 1 The structure diagram of the reaction system used in the preparation process of the super-branched chain high-performance environmentally friendly phthalate plasticizer provided by the present application;

[0048] Figure 2 The TGA thermogravimetric curve in Test Example 2;

[0049] Figure 3A weight loss curve graph in Test Example 2;

[0050] Figure 4 An infrared spectrum graph in Test Example 2.

[0051] Legend: 1 - reactor; 2 - packed column; 3 - condenser; 4 - alcohol water separation tank; 5 - filter; 6 - tank. DETAILED DESCRIPTION

[0052] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below. If specific conditions are not indicated in the embodiments, conventional conditions or conditions suggested by manufacturers are adopted. If the manufacturers of the reagents or instruments used are not indicated, they are all conventional products that can be purchased on the market.

[0053] The hyperbranched chain high-performance environmentally friendly phthalate plasticizer, the PVC product and the preparation method and application thereof provided by the present application will be described in detail below.

[0054] The present application provides a hyperbranched chain high-performance environmentally friendly phthalate plasticizer, which is obtained by esterification and polycondensation of a polybasic acid and mixed diols in the presence of a catalyst, and is terminated by a monohydric alcohol.

[0055] The hyperbranched chain high-performance environmentally friendly phthalate plasticizer has good compatibility with PVC and high plasticizing efficiency.

[0056] For example, the polybasic acid may include trimellitic anhydride (abbreviated as "TMA"), the mixed diols may include at least two of methylpropanediol (abbreviated as "MPDO"), neopentyl glycol (abbreviated as "NPG"), ethylene glycol (abbreviated as "EG") and propylene glycol (abbreviated as "1,2-PG"), and the monohydric alcohol may include at least one of isooctanol (abbreviated as "2-EH"), isononyl alcohol (abbreviated as "INA") and isodecanol (abbreviated as "2-PH").

[0057] In some preferred embodiments, the mixed diols include ethylene glycol and neopentyl glycol.

[0058] For reference, taking the polybasic acid as trimellitic anhydride, the mixed diols as ethylene glycol and neopentyl glycol, and the monohydric alcohol as isooctanol as an example, the corresponding reaction equation is as follows:

[0059] m +x +y +n

[0060] +2mH2O.

[0061] The above trimellitic anhydride is a triacid, and a polymerization reaction occurs with dihydric alcohol, and the product obtained by end-capping with monohydric alcohol belongs to a network structure. According to different molar ratios of triacid to dihydric alcohol, trimellitic polyester plasticizers with different viscosities can be prepared.

[0062] For reference, the molar ratio of the mixed dihydric alcohol to the polybasic acid can be 0.85-1.5:2, such as 0.85:2, 0.9:2, 0.95:2, 1:2, 1.05:2, 1.1:2, 1.15:2, 1.2:2, 1.25:2, 1.3:2, 1.35:2, 1.4:2, 1.45:2, or 1.5:2, etc., or any other value within the range of 0.85-1.5:2.

[0063] It should be noted that the amount of mixed dihydric alcohol has a significant effect on the viscosity of the product. The amount of polybasic acid is controlled at a certain fixed value. Under this condition, the more the amount of mixed dihydric alcohol, the higher the viscosity of the product. By controlling the molar ratio of mixed dihydric alcohol to polybasic acid within the above preferred or more preferred range, a plasticizer with a more suitable viscosity (at 25°C) can be obtained.

[0064] In this application, the amounts of each dihydric alcohol in the mixed dihydric alcohol can be equal. For example, the mixed dihydric alcohol is composed of ethylene glycol and neopentyl glycol, i.e., the molar ratio of ethylene glycol to neopentyl glycol is 1:1. In addition, the ratio of each dihydric alcohol in the mixed dihydric alcohol can be adjusted according to actual conditions.

[0065] For reference, the amount of monohydric alcohol is 150-200wt% of the polybasic acid, such as 150wt%, 160wt%, 170wt%, 180wt%, 190wt%, or 200wt%, etc., or any other value within the range of 150-200wt%.

[0066] By controlling the amount of monohydric alcohol within the above range, a plasticizer with good quality (such as viscosity, etc.) can be obtained.

[0067] For reference, the catalyst used in this application can include (be) titanium isopropylate.

[0068] The amount of catalyst added can be 0.05-0.30wt% of the polybasic acid, such as 0.05wt%, 0.10wt%, 0.15wt%, 0.20wt%, 0.25wt%, or 0.30wt%, etc., or any other value within the range of 0.05-0.30wt%, preferably 0.15-0.20wt%.

[0069] It should be noted that without adding catalyst, the reaction between the mixed diols and the polybasic acid is difficult to complete. With the increase of the amount of catalyst, the reaction time gradually shortens. When the amount of catalyst is 0.15-0.20% of the mass of the polybasic acid, it is more appropriate.

[0070] In some alternative embodiments, the hyperbranched chain high-performance environmentally friendly phthalate plasticizer has at least the following characteristics:

[0071] Appearance: colorless or slightly yellowish viscous transparent liquid; color number: ≤100 Pt-Co; heating loss: ≤0.2wt%; viscosity (25℃): 3000-4000 mPa·s; density (25℃): 1.00-1.05 g / ml; acid value: ≤1.5 mg KOH / g; hydroxyl value: ≤10 mg KOH / g; flash point: ≥260℃; number average molecular weight: 900-1100 g / mol; weight average molecular weight: 1400-1600 g / mol; polydispersity index (PDI): 1.25-1.80.

[0072] Correspondingly, the application also provides a preparation method of the above-mentioned hyperbranched chain high-performance environmentally friendly phthalate plasticizer, which may comprise the following steps: esterification and polycondensation of the polybasic acid and the mixed diols in the presence of a catalyst and end-capping by a monohydric alcohol.

[0073] Please refer to Figure 1 The reaction system involved in the above reaction process includes a reactor 1, a packed tower 2, a condenser 3, an alcohol-water separation tank 4, a filter 5, and a storage tank 6.

[0074] The reactor 1 is provided with a first inlet, a second inlet, a third inlet, a first outlet, and a second outlet. The first inlet is used for introducing the polybasic acid, the dihydric alcohol, and the monohydric alcohol, the second inlet is used for introducing a protective gas or vacuum, the third inlet and the first outlet are connected with the packed tower 2 (i.e., the reactor 1 and the packed tower 2 are bidirectionally connected), and the second outlet is connected with the filter 5.

[0075] The filter 5 has two inlets, one of which is used for introducing a filter aid, and the other of which is connected with the second outlet of the reactor 1. The filter 5 also has two outlets, one of which is used for discharging filter residue, and the other of which is used for connecting with the storage tank 6.

[0076] The packed tower 2 has two inlets, one of which is connected with the first outlet of the reactor 1, and the other of which (located at the top of the packed tower 2) is connected with the outlet of the alcohol-water separation tank 4 to recover part of the alcohol separated from the alcohol-water separation tank 4 (the remaining part of the alcohol is also used to generate water). The packed tower 2 also has two outlets, one of which is connected with the third inlet of the reactor 1, and the other of which is connected with the inlet of the condenser 3.

[0077] The outlet of the condenser 3 is connected with the alcohol-water separation tank 4, and the condenser 3 can be subjected to vacuumizing treatment.

[0078] It should be noted that the working principles of each device or apparatus involved in the above reaction system can be referred to the related prior art, and will not be described in detail here.

[0079] For reference, the above reaction process includes a temperature rising stage, an atmospheric pressure reaction stage and a negative pressure reaction stage in sequence.

[0080] In the temperature rising stage, the temperature after rising is 180-200℃ (such as 180℃, 185℃, 190℃, 195℃ or 200℃, etc.). In the temperature rising process, the head temperature of the packed column 2 is controlled to be 90-110℃ (such as 90℃, 92℃, 95℃, 98℃ or 100℃, etc.) to discharge the water generated in the reaction system, so as to promote the forward reaction. The temperature in the atmospheric pressure reaction stage is 215-220℃ (such as 215℃, 216℃, 217℃, 218℃, 219℃ or 220℃, etc.). When the acid value of the reaction system reaches 15-20 (such as 15, 16, 17, 18, 19 or 20, etc.) in the atmospheric pressure reaction process, the negative pressure reaction is adjusted to be carried out under vacuum condition (that is, it can be understood that: in the terminal stage of the reaction, the vacuum is slowly opened to full vacuum, and the negative pressure polycondensation reaction is carried out, while the excess alcohol is extracted, and the reaction progress is monitored by the indicators such as acid value and viscosity to determine the reaction endpoint).

[0081] Except for the negative pressure reaction stage, the rest of the reaction process is preferably carried out under the condition of protective atmosphere (such as nitrogen atmosphere or argon atmosphere, etc.). After the negative pressure reaction, the temperature is lowered to 70-80℃ (such as 70℃, 72℃, 75℃, 78℃ or 80℃, etc.), and the filter 5 is used for purification treatment, so as to obtain the high molecular polyester plasticizer product which meets the technical specifications and the environmental regulation control limit value.

[0082] Under the protection of inert gas such as nitrogen, the experimental device is used to synthesize the polyester plasticizer by esterification, polycondensation and monohydric alcohol end-capping of trimellitic anhydride and mixed dihydric alcohol under the action of catalyst and stirring, and slowly rising the temperature to 215-220℃. In the terminal stage of the experiment, the vacuum is slowly opened to full vacuum, and the negative pressure polycondensation reaction is carried out, while the excess alcohol is extracted, and the reaction progress is monitored by the indicators such as acid value and viscosity to determine the reaction endpoint.

[0083] In some specific embodiments, the following steps can be specifically referred to:

[0084] S1: A clean and dry reactor 1 is prepared, and the packed column 2, the condenser 3 and the alcohol-water separation tank 4 are connected, and the pressure is adjusted to 0.1 MPa for 12 hours to check and confirm the sealing of the device.

[0085] S2: The ingredients are prepared according to the formula, and the liquid is first added, and then the solid is added.

[0086] S3: warming stage: slowly warming (for example, warming at a rate of 8-12℃ per 20 min) to 180-200℃, with the head temperature controlled at 100±10℃, and the water generated by the reaction system being removed in time, to promote the forward reaction.

[0087] S4: atmospheric pressure reaction: adding a catalyst, and controlling the polycondensation reaction at 215-220℃, until the acid value reaches 15-20, and switching to vacuum reaction conditions.

[0088] S5: negative pressure reaction: controlling the reaction temperature at 215-220℃, slowly opening the vacuum, until full vacuum, and continuing the polycondensation reaction, while removing excess alcohol, and testing the acid value, viscosity and other indicators to determine the reaction endpoint, and ending the reaction.

[0089] S6: purification treatment and material transfer: cooling to 70-80℃, and performing purification treatment through filter 5, to obtain a plasticizer product that meets the technical specifications and environmental regulation control specifications.

[0090] Except for the negative pressure reaction stage, the whole process is protected by a protective atmosphere (such as a nitrogen atmosphere or an argon atmosphere), to obtain better product color.

[0091] In the present application, in the initial stage of the polymerization reaction (warming stage), the reaction mainly occurs between monomers and monomers or monomers and oligomers. Since the monomer concentration is large, the generated water is removed from the reaction system in time during the reaction process, the reverse reaction speed is relatively small, and the forward reaction speed is fast. Most of the monomers are first converted into oligomers, and the reaction can be carried out quickly without a catalyst.

[0092] The middle stage of the polymerization reaction (atmospheric pressure reaction stage) is the main stage for forming high molecular weight polycondensates. At this time, the monomer content is very small, and has been converted into condensates with different polymerization degrees. In order to break the reaction balance and make the polymer reaction proceed in the forward direction, so as to increase the molecular weight, a higher temperature and vacuum decompression method are adopted to remove small molecule products from the polymer clock.

[0093] The termination stage of the polymerization reaction (negative pressure reaction stage), the product molecular weight increases, the viscosity significantly increases, and most of the small molecules have been removed from the system. At this time, the reaction basically meets the requirements of the final polymerization, and the polymerization reaction is terminated to avoid various possible side reactions, so as to obtain a polyester product with high purity and good color.

[0094] In addition, the present application also provides a PVC product containing the above-mentioned hyperbranched chain high-performance environmentally friendly phthalate plasticizer.

[0095] Further, the PVC product also contains a PVC material and an auxiliary agent.

[0096] For reference, the above-mentioned additives may include, for example, at least one of a stabilizer, a filler, a lubricant, and an antioxidant.

[0097] wherein the type of the PVC material may exemplarily but non-limitatively include at least one of S-70 and S-65. The stabilizer may exemplarily but non-limitatively include a calcium-zinc stabilizer. The filler may exemplarily but non-limitatively include calcium carbonate. The lubricant may exemplarily but non-limitatively include PE wax. The antioxidant may exemplarily but non-limitatively include antioxidant 1010.

[0098] In the PVC product, 100 parts of the PVC material, 60-70 parts (e.g., 60 parts, 62 parts, 64 parts, 76 parts, 78 parts, or 70 parts, etc.) of the hyperbranched chain high-performance environmentally friendly phthalate plasticizer, 3-7 parts (e.g., 3 parts, 4 parts, 5 parts, 6 parts, or 7 parts, etc.) of the stabilizer, 50-60 parts (e.g., 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, or 60 parts, etc.) of the filler, 0.3-0.8 parts (e.g., 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, or 0.8 parts, etc.) of the lubricant, and 0.2-0.7 parts (e.g., 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, or 0.7 parts, etc.) of the antioxidant may be included.

[0099] In some specific embodiments, the PVC product may include 100 g of PVC (S-70), 65 g of the plasticizer provided herein, 5 g of calcium-zinc stabilizer, 53 g of calcium carbonate, 0.5 g of PE wax, and 0.4 g of antioxidant 1010.

[0100] The PVC product containing the above-mentioned hyperbranched chain high-performance environmentally friendly phthalate plasticizer has good compatibility in the PVC product and good coupling coordination with other additives due to its special hyperbranched chain network structure, which forms a heterostructure with the crosslinked grafted polymer material in the PVC product, thereby making the product have excellent application performance such as aging resistance, migration resistance, extraction resistance, non-volatility, and durability.

[0101] In some embodiments, the PVC product provided herein has the following characteristics:

[0102] Specific gravity ≤ 1.45 g / cm 3 ; Shore hardness: 80 ± 3A; tensile strength before aging ≥ 10.3 MPa; elongation at break before aging ≥ 100%; tensile strength residual rate after aging ≥ 85%; elongation at break residual rate after aging ≥ 45%; tensile strength residual rate after oil aging ≥ 75%; elongation at break residual rate after oil aging ≥ 75%; volume resistivity before immersion ≥ 1 × 10 10 Ω·m; volume resistivity after immersion ≥ 1 × 10 10 Ω·m; thermal stability at 200°C ≥ 60 minutes; passing non-migration test.

[0103] That is, the PVC product has excellent aging resistance, volatile resistance, oil extraction resistance, electrical insulation, and excellent migration resistance to ABS and PS plates.

[0104] Correspondingly, the application further provides a preparation method of the PVC product, which can include the following steps: mixing and kneading raw materials, tabletting, and tabletting.

[0105] For example, the mixing and kneading can be performed at 160-170°C (such as 162°C, 165°C, 168°C, or 170°C) for 3-5 min (such as 3 min, 3.5 min, 4 min, 4.5 min, or 5 min).

[0106] The tabletting can be performed at 180-190°C (such as 180°C, 183°C, 187°C, or 190°C) and a flat plate vulcanizing machine pressure of 45-55 tons (such as 45 tons, 48 tons, 50 tons, 52 tons, or 55 tons) for 30 s-5 min (such as 30 s, 1 min, 2 min, 3 min, 4 min, or 5 min).

[0107] It should be noted that the preparation conditions and processes of the PVC product not described in detail in the application can refer to related prior art, and will not be described in detail here.

[0108] In addition, the application further provides the application of the PVC product, which can be used to prepare wire and cable, electrical tape, gas pipe, rubber cloth, leather, and motor vehicle rubber pad, film, beverage hose, dairy machinery rubber pad, or bottle cap rubber pad.

[0109] The features and properties of the application are further described in detail in the following embodiments.

[0110] The specifications and brands of the following raw materials are as follows:

[0111] Isophthalic anhydride: industrial pure (97.0%), 25 kg / bag, Shanghai Yinn Chemical Technology Co., Ltd.;

[0112] Isopropyl alcohol: industrial pure (99.2%), 25 L / barrel, Shandong Liao Cheng Luxi Polyol New Material Technology Co., Ltd.;

[0113] Neopentyl glycol: industrial pure (99.6%), 25 L / bag, LG Chemical. Ltd;

[0114] Ethylene glycol: industrial pure (98.0%), 25 L / barrel, DAIREN Chemical Corporation;

[0115] Tetraisopropyl titanate: Industrial grade (26.5-27.8%), 500ml / bottle.

[0116] Example 1

[0117] This embodiment provides a reaction system for a hyperbranched, high-performance, environmentally friendly, polyvinylidene phthalate (PVP) polyester plasticizer. Please refer to [reference needed]. Figure 1 The reaction system includes a reactor 1, a packed tower 2, a condenser 3, an alcohol-water separator 4, a filter 5, and a storage tank 6.

[0118] Reactor 1 is provided with a first inlet, a second inlet, a third inlet, a first outlet, and a second outlet. The first inlet is used to introduce polybasic acids, diols, and monohydric alcohols; the second inlet is used to introduce protective gas or vacuum; the third inlet and the first outlet are both connected to the packed tower 2 (that is, there is a bidirectional connection between reactor 1 and packed tower 2); and the second outlet is connected to the filter 5.

[0119] Filter 5 has two inlets, one for introducing filter aid and the other connected to the second outlet of reactor 1. Filter 5 also has two outlets, one for discharging filter cake and the other for connecting to storage tank 6.

[0120] The packed tower 2 has two inlets, one of which is connected to the first outlet of reactor 1, and the other inlet (located at the top of the packed tower 2) is connected to the outlet of alcohol-water separator 4 to recover a portion of the alcohol separated in alcohol-water separator 4 (the remaining alcohol is also used to produce water in the reaction). The packed tower 2 also has two outlets, one of which is connected to the third inlet of reactor 1, and the other outlet is connected to the inlet of condenser 3.

[0121] The outlet of condenser 3 is connected to alcohol-water separator 4, and condenser 3 can be vacuumed.

[0122] Example 2

[0123] This embodiment provides a hyperbranched, high-performance, environmentally friendly, polyvinylidene polyester plasticizer, which is prepared by the following method (the reaction system used is provided in Example 1):

[0124] S1: Prepare a clean and dry reactor 1, connect the packed tower 2, condenser 3, and alcohol-water separator 4, pressurize to 0.1 MPa and maintain for 12 hours to check and confirm the airtightness of the device.

[0125] S2: Add materials according to the formula, first add liquid materials, then add solid materials.

[0126] The raw materials include a polybasic acid, a mixed dihydric alcohol, and a monohydric alcohol. The polybasic acid is trimellitic anhydride, the mixed dihydric alcohol is ethylene glycol and neopentyl glycol, and the monohydric alcohol is isooctanol. The amount of the monohydric alcohol is 170 wt% of the polybasic acid; the molar ratio of the mixed dihydric alcohol to the polybasic acid is 1.25:2; and the molar ratio of ethylene glycol to neopentyl glycol in the mixed dihydric alcohol is 1:1.

[0127] S3: warming-up stage: slowly warming up (warming up at a rate of 10℃ per 20 min) to 190℃, the head temperature is controlled at 100℃, and the water generated in the reaction system is discharged in time to promote the forward reaction.

[0128] S4: normal pressure reaction: adding a catalyst, and controlling the polycondensation reaction at 215-220℃, until the acid value reaches 18, and switching to vacuum reaction conditions.

[0129] The catalyst is titanium tetraisopropoxide, and the amount of the catalyst added is 0.2 wt% of the polybasic acid.

[0130] S5: negative pressure reaction: the reaction temperature is controlled at 215-220℃, the vacuum is slowly opened to full vacuum, and the polycondensation reaction is continued, while the excess alcohol is extracted, and the end point of the reaction is determined by testing the acid value, viscosity, and other indicators, and the reaction is ended.

[0131] S6: purification treatment and material transfer: cooling to 75℃, and performing purification treatment through a filter 5 to obtain a plasticizer product that meets the technical specifications and environmental regulation control specifications.

[0132] The above-mentioned negative pressure reaction stage is protected by a nitrogen atmosphere throughout to obtain better product color.

[0133] Example 3

[0134] The PVC sheet provided in this example contains 100g of PVC (S-70), 65g of the plasticizer provided in Example 2, 5g of a calcium-zinc stabilizer (CH401), 53g of calcium carbonate, 0.5g of PE wax, and 0.4g of an oxidant 1010.

[0135] The PVC sheet is prepared by mixing, pressing, and sheeting the above-mentioned raw materials.

[0136] The mixing is plasticizing at 165℃ for 4 min. The pressing is performed at 185℃ and a flat plate vulcanizing machine pressure of 50 tons for 2 min.

[0137] Example 4

[0138] A PVC sheet was prepared by mixing, sheeting and sheeting the above raw materials.

[0139] The PVC sheet was prepared by mixing, sheeting and sheeting the above raw materials.

[0140] The mixing was performed at 160°C for 5 minutes. The sheeting was performed at 180°C and 45 tons of flat press for 5 minutes.

[0141] Example 5

[0142] A PVC sheet was prepared by mixing, sheeting and sheeting the above raw materials.

[0143] The PVC sheet was prepared by mixing, sheeting and sheeting the above raw materials.

[0144] The mixing was performed at 170°C for 3 minutes. The sheeting was performed at 190°C and 55 tons of flat press for 30 seconds.

[0145] Test Example 1

[0146] The product of the plasticizer provided in Example 2 was subjected to physical and chemical analysis, and the test method and test results are shown in Table 1.

[0147] Table 1: Results of physical and chemical analysis of plasticizer

[0148]

[0149]

[0150] Test Example 2

[0151] The PVC product provided in Example 3 and commercially available straight-chain aliphatic polyester plasticizer A and straight-chain aliphatic polyester plasticizer B were subjected to performance comparison, and the performance test method and test results are shown in Table 2.

[0152] Table 2: Results of performance of PVC product

[0153]

[0154]

[0155] As can be seen from Table 2, compared with linear polyester plasticizer, the PVC sheet modified by the hyperbranched polyester plasticizer provided by the application has superior high-temperature aging resistance and electrical insulation performance, outstanding oil extraction resistance, migration resistance, volatility resistance, and thermal stability, etc.

[0156] In addition, the thermogravimetric and thermal differential properties of the PVC product modified by the hyperbranched polyester plasticizer in Example 3 were determined by using a METTLER TOLEDO thermal gravimetric analyzer, with a temperature rising process of 30.0-850.0℃, 20.00K / min, N2flow rate of 50.0ml / min, and the results are shown in Figure 2 and Figure 3 .

[0157] As can be seen from the TGA thermogravimetric curve of Figure 2 , the thermal weight loss of the sample in the temperature range of 200-600℃ changes: within 300℃, the polyester plasticizer has almost no mass change, and has good processing and application performance. As can be seen from the weight loss curve of Figure 3 , the decomposition temperature of the product is 318℃, which is between 300-400℃, and the weight loss is about 55%.

[0158] Further, the hyperbranched polyester plasticizer modified PVC product obtained in Example 3 was subjected to infrared spectrum test, and the infrared spectrum diagram is shown in Figure 4 . As can be seen from Figure 4 , the absorption peaks of the product at 3447cm -1 are hydroxyl absorption peaks, which are speculated to be caused by the free hydroxyl group at one end of the dihydric alcohol not being esterified with carboxyl group or the monohydric alcohol not being able to react and not being able to evaporate, which is caused by the esterification and polymerization reaction being reversible reactions accompanied by a small amount of by-products. The absorption peaks at 2918cm -1 are strong absorption peaks of C-H stretching vibration, the product has strong stretching vibration absorption peaks of ester carbonyl group at 1730cm -1 , and strong stretching vibration absorption peaks of ester C-O at 1170cm -1 , which are important evidence that the product contains ester structure.

[0159] Test Example 3

[0160] Taking Example 2 as an example, the amount of trimellitic anhydride was fixed at 2mol, and the viscosity of the plasticizer obtained by reacting dihydric alcohol with trimellitic anhydride at different molar ratios under the condition of 25℃ was studied, and the results are shown in Table 3.

[0161] Table 3 Relationship between raw material molar ratio and product viscosity

[0162] Moles of diol, mol 0.70 0.85 0.95 1.00 1.25 1.50 Viscosity at 25°C, mPa.s 800 2000 3500 4500 12000 20000

[0163] As can be seen from Table 3, the molar ratio of trimellitic anhydride to dihydric alcohol has a significant effect on the viscosity of the product. The higher the proportion of dihydric alcohol, the higher the viscosity value, and the viscosity is positively correlated. The viscosity is too high and is not suitable for poor processability.

[0164] Test Example 4

[0165] Taking Example 2 as an example, the effect of different reaction temperatures (corresponding to the reaction temperature of the atmospheric reaction stage) on the quality (color number) of the plasticizer and the reaction time was studied, and the results are shown in Table 4.

[0166] Table 4 Effect of different reaction temperatures on product color and time

[0167] Reaction temperature (°C) 205 212 220 235 Time taken (hours) 25:00 24 20:00 17:00 Product colour number (Pt-Co) 40 45 50 100

[0168] As can be seen from Table 4, the higher the reaction temperature, the shorter the reaction time, but the color number of the product becomes deeper; the lower the reaction temperature, the longer the reaction time. The suitable reaction temperature is 220°C.

[0169] Test Example 5

[0170] Taking Example 2 as an example, the molar ratio of trimellitic anhydride to dihydric alcohol was set to 2:0.95, the amount of monohydric alcohol was 180wt% of the polybasic acid, and the reaction temperature was 220°C. The effect of the amount of catalyst on the reaction time was studied, and the results are shown in Table 5.

[0171] Table 5 Effect of different catalyst amounts on reaction time

[0172] Catalyst as % of trimellitic anhydride mass 0.00 0.05 0.10 0.15 0.20 0.25 0.30 Time taken (hours) 40:00 + ]] 23:00 21:00 20:00 19:50 19:30 19:30

[0173] As can be seen from Table 5, without adding catalyst, the reaction is difficult to complete. With the increase of the amount of catalyst, the reaction time gradually shortens, and when the amount of catalyst reaches 0.25%, the reaction time does not significantly shorten. The amount of catalyst is 0.15-0.25% of the mass of trimellitic anhydride, which is more suitable.

[0174] In summary, the hyperbranched chain high-performance environmentally friendly trimellitic polyester plasticizer provided by the present application has good compatibility with PVC, good color, and good performance indicators such as viscosity, density, and acid value. It does not contain environmental control substances such as o-phenyl or DOA, and meets the requirements of various environmental regulations. When used in PVC products, the PVC products not only have excellent aging resistance and electrical insulation properties, but also have outstanding oil extraction resistance, migration resistance, volatility resistance, and thermal stability.

[0175] The above merely describes the preferred embodiments of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A PVC article, characterized in that, The PVC product contains 100 g of PVC, 65 g of the hyperbranched chain high-performance environmentally friendly phthalate plasticizer, 5 g of calcium-zinc stabilizer, 53 g of calcium carbonate, 0.5 g of PE wax, and 0.4 g of oxidant 1010 by mass fraction; The hyperbranched chain high-performance environmentally friendly phthalate plasticizer is prepared by a reaction system through the following method: The reaction system of the hyperbranched chain high-performance environmentally friendly phthalate plasticizer comprises a reactor, a filler tower, a condenser, an alcohol-water separation tank, a filter, and a storage tank; The reactor is provided with a first inlet, a second inlet, a third inlet, a first outlet, and a second outlet; the first inlet is used for introducing polybasic acid, dibasic alcohol, and monohydric alcohol, the second inlet is used for introducing protective gas or vacuum, the third inlet and the first outlet are connected with the filler tower, and the second outlet is connected with the filter; The filter has two inlets, one of which is used for introducing filter aid, and the other is connected with the second outlet of the reactor; the filter also has two outlets, one of which is used for discharging filter residue, and the other is used for connecting with the storage tank; The filler tower has two inlets, one of which is connected with the first outlet of the reactor, and the other is connected with the outlet of the alcohol-water separation tank to recover part of the alcohol separated by the alcohol-water separation tank; the filler tower also has two outlets, one of which is connected with the third inlet of the reactor, and the other is connected with the inlet of the condenser; The outlet of the condenser is connected with the alcohol-water separation tank, and the condenser can be subjected to vacuumizing treatment; The method comprises: S1: Prepare a clean and dry reactor, connect the filler tower, the condenser, and the alcohol-water separation tank, and pressurize to 0.1 MPa for 12 hours to check and confirm the sealing of the device; S2: Add raw materials according to the formula, first add liquid, and then add solid; The raw materials include polybasic acid, mixed dibasic alcohol, and monohydric alcohol; the polybasic acid is trimellitic anhydride, the mixed dibasic alcohol is ethylene glycol and neopentyl glycol, and the monohydric alcohol is isooctanol; the amount of monohydric alcohol is 170wt% of polybasic acid; the molar ratio of mixed dibasic alcohol to polybasic acid is 1.25:2; the molar ratio of ethylene glycol to neopentyl glycol in the mixed dibasic alcohol is 1:1; S3: Temperature rising stage: slowly raise the temperature at a rate of 10℃ per 20min to 190℃, control the distillation head temperature at 100℃, and timely discharge the water generated by the reaction system to promote the forward reaction; S4: Atmospheric pressure reaction: add catalyst, control the polycondensation reaction at 215-220℃, and acid value reaches 18, switch to vacuum reaction condition; The catalyst is titanium tetraisopropylate, and the addition amount is 0.2wt% of polybasic acid; S5: Negative pressure reaction: the reaction temperature is controlled at 215-220℃, slowly open the vacuum to full vacuum, continue the polycondensation reaction, and at the same time, extract the excess alcohol, test the acid value, viscosity and other indicators to determine the reaction endpoint, and end the reaction; S6: Purification treatment and material transfer: cool to 75℃, and purify through the filter to obtain the plasticizer product.

2. The method of producing a PVC article according to claim 1, characterized in that, The method comprises the following steps: mixing, sheeting, and sheeting the raw materials for preparing the PVC product.

3. The preparation method according to claim 2, characterized in that, The mixing is plasticized at 160-170℃ for 3-5min.

4. The preparation method according to claim 2, characterized in that, Tabletting was performed at 180-190°C and a press force of 45-55 tons for 30 seconds to 5 minutes.

5. Use of a PVC article according to claim 1, characterized in that, The PVC products are used to produce electric wire and cable, electrical tape, gas pipe, rubberized fabric, leather and rubber mat for motor vehicle, film, beverage hose, dairy machinery rubber mat or bottle cap rubber mat.

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