WO2018072747A1 - 聚酯组合物及其制备方法 - Google Patents

聚酯组合物及其制备方法 Download PDF

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Publication number
WO2018072747A1
WO2018072747A1 PCT/CN2017/107108 CN2017107108W WO2018072747A1 WO 2018072747 A1 WO2018072747 A1 WO 2018072747A1 CN 2017107108 W CN2017107108 W CN 2017107108W WO 2018072747 A1 WO2018072747 A1 WO 2018072747A1
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Prior art keywords
polyester composition
weight
aliphatic
aromatic copolyester
repeating unit
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PCT/CN2017/107108
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English (en)
French (fr)
Inventor
郑萃
祝桂香
刘立志
张伟
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to CA3040992A priority Critical patent/CA3040992C/en
Priority to EP17861400.4A priority patent/EP3530692A4/en
Priority to US16/343,704 priority patent/US11053385B2/en
Priority to JP2019521116A priority patent/JP7171556B2/ja
Publication of WO2018072747A1 publication Critical patent/WO2018072747A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/006—PBT, i.e. polybutylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the present invention relates to the field of polymers, and in particular to a polyester composition and a process for the preparation of the polyester composition, and a toughened composite material prepared from the polyester composition.
  • Polybutylene terephthalate is one of the five engineering plastics. It was first synthesized by German scientist P. Schlack in 1942 and then industrially developed by Celanese (now Ticona). Celanex is listed. PBT has the characteristics of good dimensional stability, high temperature resistance, excellent flame retardant and insulation properties, good fluidity, small linear thermal expansion coefficient and excellent chemical solvent resistance. It has a wide range of applications in the electrical and electronic industry, automotive industry and office machinery. . However, the impact resistance of PBT is very poor, especially sensitive to defects. A small gap on the surface of the product may cause the whole product to be chipped. Therefore, it is necessary to toughen and modify PBT.
  • the toughening modification of PBT is mainly blending modification, and it is mainly divided into three categories.
  • the first type is fiber toughening, mainly adding glass fiber to PBT, and also adding other fibers such as carbon fiber, bamboo fiber or flax fiber.
  • the main disadvantage of adding fibers is that the materials can no longer be processed using conventional injection molding processes, and often require additional processing costs, especially for long fibers with significant performance improvements, and the cost of the process is significant.
  • the second category is the addition of high impact materials. Due to the high processing temperatures of PBT, it is often necessary to add materials that can withstand higher processing temperatures.
  • a very common example is the addition of PC (polycarbonate).
  • PC polycarbonate
  • the toughness is improved.
  • the disadvantage of adding high-impact materials is that almost all current high-impact materials are incompatible with PBT, which repel each other at the molecular level, and it is difficult to fully mix even after very strong blending conditions. Adding a large amount of compatibilizer can partially solve this problem, but at the same time it will bring about a decline in material properties.
  • the third category is joining and PBT Other materials with a very similar molecular structure but stronger toughness to slightly enhance the toughness of PBT, a typical example is PET (polyethylene terephthalate).
  • the material obtained has stronger toughness than PBT.
  • the disadvantage of this type of method is that the material with similar structure to PBT has a toughness that is even better than PBT.
  • the final result is that the toughness of the obtained composite material has not been significantly improved.
  • Another effective method for the blending toughening modification of PBT is to blend and modify PBT using a copolymer containing a group similar to the PBT structure.
  • a copolymer containing a group similar to the PBT structure is limited to various reasons, such as material properties and cost control, and there is no modified material for blending PBT and corresponding copolymers on the market. Therefore, there is an urgent need to find a toughened modified PBT product.
  • the toughness of the polyester compositions and composites of the present invention should be significantly improved compared to PBT without substantial loss of strength.
  • Another object of the invention is to improve the compatibility of PBT with other components in the polyester composition so that no additional compatibilizer is required.
  • Another object of the present invention is to provide a polyester composition which can be processed using the same equipment as PBT without the need for additional modifications to the processing equipment during its preparation.
  • the above object is achieved by a polyester composition comprising PBT and a specific aliphatic-aromatic copolyester.
  • the present invention provides a polyester composition
  • a polyester composition comprising
  • aliphatic-aromatic copolyester is a copolymer comprising a repeating unit A represented by the formula (I) and a repeating unit B represented by the formula (II),
  • the content of the repeating unit A is from 1 to 60 mol%, preferably from 20 to 55 mol%, based on the total moles of the repeating unit A and the repeating unit B in the aliphatic-aromatic copolyester. More preferably, it is 20-40 mol%, and the content of the repeating unit B is 40-99 mol%, preferably 45-80 mol%, more preferably 60-80 mol%; m is an integer of 2-10, and n is 2-8.
  • An integer, p is an integer from 2 to 10, preferably m is an integer from 2 to 6, an integer of 2-4, p is an integer from 2 to 6, preferably from 2 to 4; and m, n and p are the same or different ;
  • weight % is calculated based on the total weight of the polybutylene terephthalate and the aliphatic-aromatic copolyester.
  • the aliphatic-aromatic copolyester has a weight average molecular weight of from 50,000 to 900,000, preferably from 100,000 to 500,000, and the weight average molecular weight is measured according to GPC; preferably, the molecular weight distribution is from 1.2 to 3, as measured by GPC.
  • the polybutylene terephthalate has a weight average molecular weight of from 100,000 to 200,000 as measured by GPC.
  • the polyester composition may further comprise a nucleating agent; the nucleating agent is present in an amount of from 0.01 to 10% by weight, preferably from 0.2 to 5% by weight, based on the total weight of the polyester composition.
  • the nucleating agent may be selected from the group consisting of talc, calcium oxide, carbon black, calcium carbonate, inorganic pigments, kaolin, metal carboxylates, metal phosphates, dibenzyl sorbitol and derivatives thereof, polyvinylcyclohexane, One or more of polyvinylcyclopentane, low density polyethylene, hyperbranched polyamide and ethylene-methacrylic acid ionomer; preferably calcium carbonate, low density polyethylene, dibenzyl sorbitol and derivatives thereof And one or more of the hyperbranched polyamides.
  • the polyester composition may also contain other additives such as erucamide and/or white oil.
  • the aliphatic-aromatic copolyester may be a random copolymer, an alternating copolymer, At least one of a block copolymer and a graft copolymer.
  • the polyester composition according to the invention may have an elongation at break of up to 230%, as measured according to the method of GB/T 1040.2-2006.
  • the present invention also provides a process for preparing a polyester composition according to the present invention, which comprises: mixing polybutylene terephthalate and an aliphatic-aromatic copolyester, and extruding the obtained mixture Granulation is carried out to obtain a polyester composition.
  • the mixing may be carried out under stirring; and, the stirring may be carried out at a rate of 6-60 rpm, and the stirring may be carried out for 2-30 min;
  • said extrusion granulation is carried out in a twin-screw extruder; preferably, said extrusion granulation conditions comprise: a temperature of 230-300 ° C, a screw speed of 10-70 rpm, a torque of 2-80 N *m.
  • the mixing process does not incorporate a compatibilizer.
  • the present invention also provides a toughened composite material prepared from the polyester composition, which has an elongation at break of up to 230% or more, as measured according to the method of GB/T 1040.2-2006.
  • the invention achieves the purpose of toughening and modifying PBT by blending PBT with an aliphatic-aromatic copolyester.
  • the polyester composition provided by the present invention has significantly improved toughness and no significant loss in strength; meanwhile, in the preparation of the polyester composition, PBT and the aliphatic-aromatic used in the present invention
  • the copolyesters have good compatibility, so no additional compatibilizer is required.
  • the polyester composition provided by the present invention can be processed using the same equipment as PBT, and no additional modification of the processing equipment is required during the preparation thereof. Therefore, the polyester composition provided by the present invention has a good industrial application prospect.
  • the present invention provides a polyester composition comprising polybutylene terephthalate and an aliphatic-aromatic copolyester, wherein the polybutylene terephthalate is used
  • the content of the polybutylene terephthalate is 50 to 99% by weight based on the total weight of the aliphatic-aromatic copolyester, and the content of the aliphatic-aromatic copolyester is 1-50% by weight.
  • the content of the polybutylene terephthalate is 70 based on the total weight of the polybutylene terephthalate and the aliphatic-aromatic copolyester. 95% by weight, the content of the aliphatic-aromatic copolyester is 5 to 30% by weight; more preferably, the content of the polybutylene terephthalate is 80 to 90% by weight, The content of the aliphatic-aromatic copolyester is from 10 to 20% by weight.
  • the aliphatic-aromatic copolyester may be a copolymer containing the repeating unit A represented by the formula (I) and the repeating unit B represented by the formula (II).
  • the content of the repeating unit A is from 1 to 60 mol%, based on the total number of moles of the repeating unit A and the repeating unit B in the aliphatic-aromatic copolyester, and the content of the repeating unit B 40-99 mol%; m is an integer of 2-10, n is an integer of 2-8, p is an integer of 2-10, and m, n and p are the same or different, the aliphatic-aromatic copolymerization
  • the ester may have a weight average molecular weight of from 50,000 to 900,000.
  • the content of the repeating unit A is from 20 to 55 mol%, more preferably from the total number of moles of the repeating unit A and the repeating unit B in the aliphatic-aromatic copolyester. 20-50% by weight; the content of the repeating unit B is 45-80% by weight, more preferably 50-80% by weight; m is an integer of 2-6, n is an integer of 2-4, and p is 2-6 An integer of from 2 to 4, and m, n and p are the same or different, and the aliphatic-aromatic copolyester may have a weight average molecular weight of from 100,000 to 500,000.
  • the weight average molecular weight of the polymer is measured by gel permeation chromatography (GPC).
  • the aliphatic-aromatic copolyester may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, preferably a random copolymer and/or Block copolymer.
  • the source of the aliphatic-aromatic copolyester of the present invention is not particularly limited and can be obtained by a conventional means in the art, for example, commercially available, or It was prepared in accordance with the method disclosed in CN100429256C.
  • the method for preparing the aliphatic-aromatic copolyester may include the following steps:
  • the monomer A is butanediol; the monomer B is terephthalic acid and/or an ester thereof, preferably terephthalic acid, dimethyl terephthalate and diethyl terephthalate At least one of the monomers C is a C2-C4 diol (particularly a saturated linear diol); the monomer D is a C4-C6 dibasic acid (especially a saturated linear two)
  • the first catalyst is at least one of tetrabutyl titanate, titanium dioxide, titanium diethoxyoxide and zinc acetate, preferably tetrabutyl titanate; the second catalyst is cesium acetylacetonate, At least one of barium trichloride, triphenyloxyanthracene and cesium propionate is preferably cesium acetylacetonate.
  • the molar ratio of the monomer B to the first catalyst is 1:0.0001-0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003.
  • the molar ratio of the monomer D to the first catalyst is 1:0.0001-0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003.
  • the total amount of the first catalyst (the sum of the amounts of the first catalysts in the step (1) and the step (2)) and the amount of the second catalyst are 1:0.5 - 1.5, preferably 1:0.8-1.2.
  • the kinds of the respective reactive monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product are separately controlled by adjusting the amount of the feed and the ratio of the feed.
  • the temperature of the reaction in the step (1), is preferably 160-220 ° C; in the present invention, in the step (2), the temperature of the reaction is preferably 160-220 ° C; In the invention, in the step (3), the temperature of the reaction is preferably from 180 to 240 °C.
  • the method for preparing the aliphatic-aromatic copolyester comprises the following steps:
  • A' is terephthalic acid and/or an ester thereof, preferably at least one of terephthalic acid, dimethyl terephthalate and diethyl terephthalate; monomer B' is C4- a dibasic acid of C6 (particularly a saturated linear dibasic acid); the first catalyst and the second catalyst are as described above and will not be further described herein.
  • the molar ratio of the monomer A' to the first catalyst is 1:0.0001-0.02:0.0001-0.02, more preferably 1:0.001-0.003:0.001-0.003 .
  • the molar ratio of the first catalyst to the second catalyst is from 1:0.5 to 1.5, preferably from 1:0.8 to 1.2.
  • the kinds of the respective reactive monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product are separately controlled by adjusting the amount of the feed and the ratio of the feed.
  • the temperature of the reaction in the step (S1), is preferably from 160 to 220 ° C; in the present invention, in the step (S2), the temperature of the reaction is preferably from 180 to 240 °C.
  • the method for producing the aliphatic-aromatic copolyester may include the steps of: adding 1,4-butanediol, dimethyl benzoate, and a catalyst as described in US Pat. No. 1,312,373 to a reactor, Heat and stir under a nitrogen atmosphere until a clear solution is obtained. Subsequently, the temperature was raised to 160-220 ° C to react. When most of the distilled methanol in the system was removed, succinic acid was added and the temperature was raised to 180-240 °C. Most of the water was distilled off, and then the vacuum was slowly added, and the temperature was raised to 220-280 ° C. After 3-6 hours, the reaction was completed to obtain a product.
  • the polybutylene terephthalate is not particularly limited and may be a conventional choice in the art, for example, the polybutylene terephthalate may have a weight average molecular weight of 100,000. -200,000, and can be obtained by conventional commercial purchase, for example, can be purchased from DuPont's Crastin SC164 NC010.
  • the polyester composition may further comprise a nucleating agent; the nucleating agent is present in an amount of from 0.01 to 10% by weight, preferably from 0.2 to 5, based on the total weight of the polyester composition % is more preferably from 1 to 5% by weight.
  • the nucleating agent may be a conventional choice in the art.
  • the nucleating agent may be selected from the group consisting of talc, calcium oxide, carbon black, calcium carbonate, and inorganic pigments (such as those purchased from Guangzhou Yingyi Plastic Pigment). Co., Ltd.
  • kaolin metal carboxylate, metal phosphate, dibenzyl sorbitol and its derivatives, polyvinylcyclohexane, polyvinylcyclopentane, low density polyethylene, hyperbranched
  • a polyamide and an ethylene-methacrylic acid ionomer preferably one or more of calcium carbonate, low density polyethylene, dibenzyl sorbitol and derivatives thereof, and hyperbranched polyamide; More preferably, it is calcium carbonate and/or low density polyethylene.
  • the polyester composition may further contain other additives, for example, erucamide and/or white oil may also be contained.
  • the present invention also provides a process for preparing a polyester composition according to the present invention, which comprises: mixing all components including polybutylene terephthalate and an aliphatic-aromatic copolyester, and The resulting mixture was subjected to extrusion granulation to obtain a polyester composition.
  • the above method may further comprise: the process of mixing the polybutylene terephthalate and the aliphatic-aromatic copolyester in the presence of a nucleating agent; and the total of the polyester composition
  • the nucleating agent may be used in an amount of from 0.01 to 10% by weight, based on the weight, preferably from 0.2 to 5% by weight, more preferably from 1 to 5% by weight.
  • nucleating agent is as described above.
  • the method may further include: the process of mixing the PBT and the aliphatic-aromatic copolyester in the presence of a nucleating agent and other additives, wherein the other additives may be erucamide and/or Or white oil.
  • the mixing can be carried out under agitation; the agitation rate can be 6-60 rpm, and the agitation time can be 2-30 min.
  • the extrusion granulation process can be carried out in accordance with a conventional extrusion granulation method, for example, the extrusion granulation can be carried out in a twin-screw extruder; preferably, the extrusion granulation
  • the conditions of the granules include: a temperature of 230-300 ° C, a screw rotation speed of 10-70 rpm, and a torque of 2-80 N*m; more preferably, the twin-screw extruder includes six temperature sections and from the feed port The temperatures to the sections of the extrusion port were 240 ° C, 250 ° C, 260 ° C, 260 ° C, 265 ° C, and 260 ° C, respectively.
  • the inventors unexpectedly discovered during the research that blending PBT with an aliphatic-aromatic copolyester can significantly improve the toughness of the product; and, copolymerization of the aliphatic-aromatic copolyester with PBT.
  • the material has good compatibility, and the purpose of toughening and modifying the PBT material can be achieved under the conventional blending conditions without additional compatibilizing agent. Therefore, in the present invention, the mixing process may be carried out without adding a compatibilizing agent.
  • the compatibilizing agent may be a conventional choice in the art, and may be, for example, PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH, and PP-g- At least one of the MAHs.
  • the polyester composition according to the present invention has an elongation at break of up to 230% or more, and the toughness is remarkably improved.
  • the toughened composite material can be prepared from the polyester composition of the present invention by a conventional molding process.
  • the toughened composite material according to the present invention may have an elongation at break of up to 230% or more, as measured according to the method of GB/T 1040.2-2006.
  • the weight average molecular weight of the polymer was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent in a Waters-208 (with a Waters 2410 RI detector, 1.5 mL/min flow rate, 30 ° C) instrument.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • Waters-208 with a Waters 2410 RI detector, 1.5 mL/min flow rate, 30 ° C
  • microstructure of PBT and aliphatic-aromatic copolyesters was determined by an AVANCE DRX 400 MHz NMR spectrometer from Bruker, Switzerland, using deuterated chloroform as a solvent;
  • the composition of the polyester composition is determined by the feeding of the raw materials
  • the mechanical properties of the polyester composition are tested according to the method of GB/T 1040.2-2006, and the 5B spline is selected for the spline;
  • the aliphatic-aromatic copolyester used in the present invention is prepared by itself according to the method disclosed in Example B13-B21 of CN100429256C, wherein the reaction can be adjusted accordingly according to the composition and molecular weight of the target product, unless otherwise specified.
  • the type of raw material, and the molecular weight of the product and the content of each repeating unit in the product are controlled by adjusting the amount of feed and the ratio of feed.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the screw torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 240.
  • the polyester composition A1 was obtained at ° C, 250 ° C, 260 ° C, 260 ° C, 265 ° C, and 260 ° C.
  • a polyester composition was prepared according to the method of Example 1, except that the butylene terephthalate-butyl succinate copolyester used in Example 1 was not added to obtain a polyester composition D1. .
  • a polyester composition was prepared according to the method of Example 1, except that the amount of polybutylene terephthalate was 20 g, and the amount of butylene terephthalate-butyl succinate copolyester was used. It was 180 g and a polyester composition D2 was obtained.
  • a polyester composition was prepared according to the method of Example 1, except that the same weight of polybutylene succinate (available from BASF, under the designation 1111HTA4) was used instead of the terephthalic acid used in Example 1. Butanediol-succinic acid butylene glycol copolyester to obtain polyester composition D3.
  • polybutylene succinate available from BASF, under the designation 1111HTA4
  • a polyester composition was prepared according to the method of Example 1, except that the same weight of polyethylene terephthalate (available from DuPont, under the designation FR530) was used instead of the p-phenylene used in Example 1.
  • the butane carboxylic acid-butyl succinate copolyester was used to prepare a polyester composition D4.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the screw torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 240.
  • the polyester composition A2 was obtained at ° C, 250 ° C, 260 ° C, 260 ° C, 265 ° C, and 260 ° C.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the screw torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was determined.
  • the polyester composition A3 was obtained by 240 ° C, 250 ° C, 260 ° C, 260 ° C, 265 ° C, and 260 ° C.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the screw torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 240.
  • the polyester composition A4 was obtained at ° C, 250 ° C, 260 ° C, 260 ° C, 265 ° C, and 260 ° C.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the screw torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 240.
  • the polyester composition A5 was obtained at ° C, 250 ° C, 260 ° C, 260 ° C, 265 ° C, and 260 ° C.
  • the polyester composition A6 was obtained at 250 ° C, 260 ° C, 260 ° C, 265 ° C, and 260 ° C.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the screw torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 240.
  • the polyester composition A7 was obtained at ° C, 250 ° C, 260 ° C, 260 ° C, 265 ° C, and 260 ° C.
  • the obtained mixture was subjected to extrusion granulation through a twin-screw extruder, the rotation speed of the screw was controlled to 10 rpm, the screw torque was 20 N*m, and the temperature in each section of the twin-screw extruder from the feed port to the extrusion port was 240.
  • the polyester composition A8 was obtained at ° C, 250 ° C, 260 ° C, 260 ° C, 265 ° C, and 260 ° C.
  • a polyester composition was prepared in the same manner as in Example 1 except that the calcium carbonate used in Example 1 was not added to obtain a polyester composition A9.
  • polyester compositions prepared in Examples 1-9 and Comparative Examples 1-4 were respectively made into stamping splines, and the prepared punched splines were subjected to mechanical property tests such as tensile yield strength (MPa) and elongation at break. The rate (%), the results are shown in Table 1 below.
  • the polyester composition provided by the present invention has an elongation at break.
  • the long rate is as high as 230%, the toughness is obviously improved, and the strength is not greatly lost.
  • no additional compatibilizer is added during the preparation of the polyester composition.
  • the polyester composition provided by the present invention can be processed using the same equipment as PBT, and no additional modification of the processing equipment is required during the preparation thereof. Therefore, the present invention
  • the polyester composition provided has good industrial application prospects.

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Abstract

本发明涉及一种聚酯组合物及其制备方法。本发明提供的聚酯组合物含有聚对苯二甲酸丁二醇酯和脂肪族-芳香族共聚酯，其中，以所述聚对苯二甲酸丁二醇酯和所述脂肪族-芳香族共聚酯的总重量为基准，所述聚对苯二甲酸丁二醇酯的含量为50-99重量％，所述脂肪族-芳香族共聚酯的含量为1-50重量％。本发明还提供了这种聚酯组合物的制备方法和由其制备的增韧的复合材料。本发明提供的聚酯组合物的断裂伸长率高达230％以上，韧性得到明显的改善，并且强度没有大幅的损失。

Description

聚酯组合物及其制备方法 技术领域
本发明涉及聚合物领域，具体地，涉及一种聚酯组合物和该聚酯组合物的制备方法，以及由该聚酯组合物制备的增韧的复合材料。
背景技术
聚对苯二甲酸丁二醇酯(PBT)是五大工程塑料之一，最早由德国科学家P.Schlack于1942年合成，之后由美国Celanese公司(现为Ticona公司)进行工业开发，并以商品名Celanex上市。PBT具有尺寸稳定性好，耐高温，阻燃和绝缘性能优异，流动性好，线性热膨胀系数小，耐化学溶剂性能优良等特点，在电子电气行业，汽车工业和办公机械领域有着十分广泛的应用。但PBT的抗冲性能很差，尤其对缺陷十分敏感，制品表面微小的缺口就可能导致整块制品的碎裂。因此，对PBT的增韧改性十分必要。
对PBT的增韧改性主要为共混改性，在其中又主要分为三类。第一类是纤维增韧，主要是向PBT中加入玻璃纤维，也有加入碳纤维、竹纤维或亚麻纤维等其它纤维的。例如，CN105086387A中，向PBT中加入约一半量的玻璃纤维，可以显著地提高其缺口冲击强度。加入纤维的主要缺点是材料不再能使用传统的注塑工艺进行加工，而往往需要额外的配套工艺成本，特别是对于性能提高显著的长纤维，工艺的成本十分明显。第二类是加入高抗冲的材料。由于PBT的加工温度较高，往往也需要加入可以耐较高加工温度的材料。一个非常常见的例子是加入PC(聚碳酸酯)。例如，CN104693759A中，向PBT中加入约自身量100％-200％的PC后，得到了韧性的提升。加入高抗冲材料的缺点是，几乎所有目前的高抗冲材料都与PBT不相容，它们在分子水平上会排斥彼此，即使经过了非常强烈的共混条件仍然难以完全混匀。大量地加入相容剂可以部分地解决这个问题，但同时会带来材料性能的下降。第三类是加入和PBT 分子结构非常近似但韧性更强的其它材料，来稍微提升PBT的韧性，一个典型的例子就是PET(聚对苯二甲酸乙二醇酯)。例如，CN104419125A中，约等量的PBT和PET共混，得到的材料较PBT有更强的韧性。这一类方式的缺点是，和PBT分子结构相近的材料，韧性即使比PBT好也是有限的，最终的结果是，得到的复合材料的韧性并没有得到显著的改善。
对PBT的共混增韧改性，另一个行之有效的方法就是使用一种含有与PBT结构相近基团的共聚物对PBT进行共混改性。然而，虽然目前含有PBT结构的共聚物已有不少，但是限于各种原因，例如材料性能和成本控制等，市场上尚没有将PBT和相应共聚物共混的改性材料。因此，目前急需寻找一种增韧改性的PBT产品。
发明内容
本发明的目的是，为了克服现有的PBT产品具有的上述缺陷，提供一种聚酯组合物及其制备方法，以及由该聚酯组合物制备的增韧的复合材料。与PBT相比，本发明的聚酯组合物和复合材料的韧性应该明显提高，并且强度没有大幅的损失。
本发明的另一目的是，改进聚酯组合物中PBT与其他组分的相容性，从而不需要额外加入相容剂。
本发明的另一目的是，提供一种聚酯组合物，其应可以与PBT使用相同的设备进行加工，在其制备的过程中无需对加工设备进行额外的改造。
根据本发明，通过包含PBT与特定的脂肪族-芳香族共聚酯的聚酯组合物而实现了上述目的。
因此，本发明提供了一种聚酯组合物，含有
(1)50-99重量％，优选70-95重量％，更优选80-90重量％的聚对苯二甲酸丁二醇酯；和
(2)1-50重量％，优选5-30重量％，更优选10-20重量％的脂肪族- 芳香族共聚酯，其中所述脂肪族-芳香族共聚酯为含有式(I)所示的重复单元A和式(II)所示的重复单元B的共聚物，
Figure PCTCN2017107108-appb-000001
Figure PCTCN2017107108-appb-000002
其中，以所述脂肪族-芳香族共聚酯中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为1-60摩尔％，优选20-55摩尔％，更优选20-40摩尔％，所述重复单元B的含量为40-99摩尔％，优选45-80摩尔％，更优选60-80摩尔％；m为2-10的整数，n为2-8的整数，p为2-10的整数，优选m为2-6的整数，n为2-4的整数，p为2-6，优选2-4的整数；且m、n和p相同或不同；
其中所述重量％以所述聚对苯二甲酸丁二醇酯和所述脂肪族-芳香族共聚酯的总重量为基准计算。
优选地，所述脂肪族-芳香族共聚酯的重均分子量为50,000-900,000，优选100,000-500,000，该重均分子量根据GPC测得；优选，分子量分布为1.2-3，由GPC测得。
优选地，所述聚对苯二甲酸丁二醇酯的重均分子量为100,000-200,000，由GPC测得。
所述聚酯组合物还可以含有成核剂；以所述聚酯组合物的总重量为基准，所述成核剂的含量为0.01-10重量％，优选为0.2-5重量％。
所述成核剂可以选自滑石粉、氧化钙、炭黑、碳酸钙、无机颜料、高岭土、羧酸金属盐、磷酸金属盐、二苄山梨醇及其衍生物、聚乙烯基环己烷、聚乙烯基环戊烷、低密度聚乙烯、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的一种或几种；优选为碳酸钙、低密度聚乙烯、二苄山梨醇及其衍生物和超支化聚酰胺中的一种或几种。
所述聚酯组合物还可以含有其他添加剂，例如芥酸酰胺和/或白油。
另外，所述脂肪族-芳香族共聚酯可以为无规共聚物、交替共聚物、 嵌段共聚物和接枝共聚物中的至少一种。
有利地，根据本发明的聚酯组合物的断裂伸长率可以高达230％以上，根据GB/T 1040.2-2006方法测得。
本发明还提供了根据本发明的聚酯组合物的制备方法，该方法包括：将聚对苯二甲酸丁二醇酯和脂肪族-芳香族共聚酯混合，并将得到的混合物进行挤出造粒，以得到聚酯组合物。
所述混合可以在搅拌的条件下进行；并且，所述搅拌的速率可以为6-60rpm，所述搅拌的时间可以为2-30min；
有利地，所述挤出造粒在双螺杆挤出机中进行；优选地，所述挤出造粒的条件包括：温度为230-300℃，螺杆转速为10-70rpm，扭矩为2-80N*m。
优选，所述混合的过程不加入相容剂。
另一方面，本发明还提供由该聚酯组合物制备的增韧的复合材料，其断裂伸长率可以高达230％以上，根据GB/T 1040.2-2006方法测得。
本发明通过将PBT与脂肪族-芳香族共聚酯共混，以达到对PBT进行增韧改性的目的。与PBT相比，本发明的提供的聚酯组合物的韧性明显提高，并且强度没有大幅的损失；同时，在该聚酯组合物的制备过程中，由于PBT与本发明使用的脂肪族-芳香族共聚酯具有很好的相容性，所以不需要额外加入相容剂。另外，本发明提供的聚酯组合物可以与PBT使用相同的设备进行加工，在其制备的过程中无需对加工设备进行额外的改造。因此，本发明提供的聚酯组合物具有良好的工业应用前景。
本发明的其它特征和优点将在随后的发明详述部分予以详细说明。
发明详述
本发明提供了一种聚酯组合物，该聚酯组合物含有聚对苯二甲酸丁二醇酯和脂肪族-芳香族共聚酯，其中，以所述聚对苯二甲酸丁二醇酯和所述脂肪族-芳香族共聚酯的总重量为基准，所述聚对苯二甲酸丁二醇酯的含量为50-99重量％，所述脂肪族-芳香族共聚酯的含量为1-50重量％。
在优选的情况下，以所述聚对苯二甲酸丁二醇酯和所述脂肪族-芳香族共聚酯的总重量为基准，所述聚对苯二甲酸丁二醇酯的含量为70-95重量％，所述脂肪族-芳香族共聚酯的含量为5-30重量％；更优选地，所述聚对苯二甲酸丁二醇酯的含量为80-90重量％，所述脂肪族-芳香族共聚酯的含量为10-20重量％。
根据本发明，所述脂肪族-芳香族共聚酯可以为含有式(I)所示的重复单元A和式(II)所示的重复单元B的共聚物，
Figure PCTCN2017107108-appb-000003
Figure PCTCN2017107108-appb-000004
其中，以所述脂肪族-芳香族共聚酯中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为1-60摩尔％，所述重复单元B的含量为40-99摩尔％；m为2-10的整数，n为2-8的整数，p为2-10的整数，且m、n和p相同或不同，所述脂肪族-芳香族共聚酯的重均分子量可以为50,000-900,000。
在优选的情况下，以所述脂肪族-芳香族共聚酯中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为20-55摩尔％，更优选为20-50重量％；所述重复单元B的含量为45-80重量％，更优选为50-80重量％；m为2-6的整数，n为2-4的整数，p为2-6，优选2-4的整数，且m、n和p相同或不同，所述脂肪族-芳香族共聚酯的重均分子量可以为100,000-500,000。
在本发明中，聚合物的重均分子量根据凝胶渗透色谱法(GPC)测得。
在本发明中，所述脂肪族-芳香族共聚酯可以为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种，优选为无规共聚物和/或嵌段共聚物。本发明对所述脂肪族-芳香族共聚酯的来源没有特别的限定，可以通过本领域的常规手段获得，例如，可以通过商购获得，或者，可 以按照CN100429256C中公开的方法制备得到。
具体地，所述脂肪族-芳香族共聚酯的制备方法可以包括以下步骤：
(1)在惰性气氛中，将单体A和单体B在第一催化剂的存在下进行反应；
(2)在惰性气氛中，将单体C和单体D在第一催化剂的存在下进行反应；
(3)将由步骤(1)得到的反应产物和由步骤(2)得到的反应产物在第二催化剂的存在下进行反应；
其中，所述单体A为丁二醇；所述单体B为对苯二甲酸和/或其酯，优选为对苯二甲酸、对苯二甲酸二甲酯和对苯二甲酸二乙酯中的至少一种；所述单体C为C2-C4的二元醇(特别是饱和直链二元醇)；所述单体D为C4-C6的二元酸(特别是饱和直链二元酸)；所述第一催化剂为钛酸四丁酯、二氧化钛、二乙氧基钛和乙酸锌中的至少一种，优选为钛酸四丁酯；所述第二催化剂为乙酰丙酮镧、三氯化镧、三苯氧基镧和丙酸镧中的至少一种，优选为乙酰丙酮镧。
在本发明中，在步骤(1)中，所述单体B与所述第一催化剂的摩尔比为1：0.0001-0.02：0.0001-0.02，更优选为1：0.001-0.003：0.001-0.003。
在本发明中，在步骤(2)中，所述单体D与所述第一催化剂的摩尔比为1：0.0001-0.02：0.0001-0.02，更优选为1：0.001-0.003：0.001-0.003。
在优选的情况下，所述第一催化剂的总用量(步骤(1)和步骤(2)中的第一催化剂的用量之和)与所述第二催化剂的用量的摩尔比为1：0.5-1.5，优选为1：0.8-1.2。
在本发明中，可以根据目标产品的组成和分子量，相应地调整各反应单体的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量。
在本发明中，在步骤(1)中，所述反应的温度优选为160-220℃；在本发明中，在步骤(2)中，所述反应的温度优选为160-220℃；在本发明中，在步骤(3)中，所述反应的温度优选为180-240℃。
在本发明优选的实施方式中，当m1为4时，所述脂肪族-芳香族共聚酯的制备方法包括以下步骤：
(S1)在惰性气氛中，将丁二醇和单体A’在第一催化剂的存在下进行反应；
(S2)将由步骤(S1)得到的反应产物和单体B’在第二催化剂的存在下进行反应；
其中，A’为对苯二甲酸和/或其酯，优选为对苯二甲酸、对苯二甲酸二甲酯和对苯二甲酸二乙酯中的至少一种；单体B’为C4-C6的二元酸(特别是饱和直链二元酸)；所述第一催化剂和所述第二催化剂如上所述，在此不再赘述。
在本发明中，在步骤(S1)中，所述单体A’与所述第一催化剂的摩尔比为1：0.0001-0.02：0.0001-0.02，更优选为1：0.001-0.003：0.001-0.003。
在优选的情况下，所述第一催化剂的用量与所述第二催化剂的用量的摩尔比为1：0.5-1.5，优选为1：0.8-1.2。
在本发明中，可以根据目标产品的组成和分子量，相应地调整各反应单体的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量。
在本发明中，在步骤(S1)中，所述反应的温度优选为160-220℃；在本发明中，在步骤(S2)中，所述反应的温度优选为180-240℃。
更具体地，所述脂肪族-芳香族共聚酯的制备方法可以包括以下步骤：将1,4-丁二醇、苯甲酸二甲酯和如US11312373中所述的催化剂加入反应器中，在氮气氛围下加热和搅拌，直至得到透明的溶液。随后，将温度升至160-220℃反应。当体系中绝大多数蒸馏出的甲醇被除去后，加入丁二酸，升温至180-240℃。蒸馏除去大部分水，然后缓慢加上真空环境，并将体系升温至220-280℃，3-6小时后反应完成，得到产品。
在本发明中，对所述聚对苯二甲酸丁二醇酯没有特别的限定，可以为本领域的常规选择，例如，所述聚对苯二甲酸丁二醇酯的重均分子量可以为100,000-200,000，并且可以通过常规的商购获得，例如可以购自 杜邦公司的Crastin SC164 NC010。
根据本发明，所述聚酯组合物还可以含有成核剂；以所述聚酯组合物的总重量为基准，所述成核剂的含量为0.01-10重量％，优选为0.2-5重量％，更优选为1-5重量％。
根据本发明，所述成核剂可以为本领域的常规选择，例如，所述成核剂可以选自滑石粉、氧化钙、炭黑、碳酸钙、无机颜料(如购自广州颖毅塑胶颜料有限公司的黄色或绿色颜料)、高岭土、羧酸金属盐、磷酸金属盐、二苄山梨醇及其衍生物、聚乙烯基环己烷、聚乙烯基环戊烷、低密度聚乙烯、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的一种或几种；优选为碳酸钙、低密度聚乙烯、二苄山梨醇及其衍生物和超支化聚酰胺中的一种或几种；更优选为碳酸钙和/或低密度聚乙烯。
在本发明中，所述聚酯组合物还可以含有其他添加剂，例如还可以含有芥酸酰胺和/或白油。
本发明还提供了根据本发明的聚酯组合物的制备方法，该方法包括：将包括聚对苯二甲酸丁二醇酯和脂肪族-芳香族共聚酯在内的所有组分混合，并将得到的混合物进行挤出造粒，以得到聚酯组合物。
根据本发明，上述方法还可以包括：将聚对苯二甲酸丁二醇酯和脂肪族-芳香族共聚酯混合的过程在成核剂的存在下进行；以所述聚酯组合物的总重量为基准，所述成核剂的用量可以为0.01-10重量％，优选为0.2-5重量％，更优选为1-5重量％。
所述成核剂的类型如上文中所述。
在本发明中，该方法还可以包括：将PBT和脂肪族-芳香族共聚酯混合的过程在成核剂和其他添加剂的存在下进行，其中，所述其他添加剂可以为芥酸酰胺和/或白油。
根据本发明，所述混合可以在搅拌的条件下进行；所述搅拌的速率可以为6-60rpm，所述搅拌的时间可以为2-30min。
根据本发明，所述挤出造粒过程可以按照常规的挤出造粒方法实施，例如，所述挤出造粒可以在双螺杆挤出机中进行；优选地，所述挤出造 粒的条件包括：温度为230-300℃，螺杆转速为10-70rpm，扭矩为2-80N*m；更优选地，所述双螺杆挤出机包括六个温度区段，且从进料口到挤出口各区段的温度依次为240℃、250℃、260℃、260℃、265℃、260℃。
在本发明中，发明人在研究过程中意外地发现：将PBT与脂肪族-芳香族共聚酯共混，可以明显提高产品的韧性；并且，脂肪族-芳香族共聚酯与PBT的共聚物具有良好的相容性，无需额外加入相容剂，在常规的共混条件下即可实现对PBT材料进行增韧改性的目的。因此，在本发明中，所述混合的过程可以不加入相容剂。
在本发明中，所述相容剂可以为本领域常规的选择，例如，可以为PE-g-ST、PP-g-ST、ABS-g-MAH、PE-g-MAH和PP-g-MAH中的至少一种。
根据本发明的聚酯组合物的断裂伸长率可高达230％以上，韧性得到明显的改善。
由本发明的聚酯组合物可以通过常规成型工艺制备增韧的复合材料。根据本发明的增韧的复合材料的断裂伸长率可以高达230％以上，根据GB/T 1040.2-2006方法测得。
具体实施方式
以下将通过实施例对本发明进行详细描述。应当理解的是，此处所描述的实施例仅用于说明和解释本发明，并不用于限制本发明。
在以下实施例和对比例中，
聚合物的重均分子量采用凝胶渗透色谱法(GPC)，以四氢呋喃(THF)为溶剂，在Waters-208(带Waters 2410 RI检测器，1.5mL/min流速，30℃)仪器上测量，以聚苯乙烯标样校准；
PBT和脂肪族-芳香族共聚酯的微观结构采用瑞士Bruker公司的AVANCE DRX 400MHz核磁共振波谱仪测定，以氘代氯仿作为溶剂；
聚酯组合物的组成通过原料的投料确定；
聚酯组合物的力学性能根据GB/T 1040.2-2006方法检测，样条选用其中的5B样条；
在没有特别说明的情况下，本发明使用的脂肪族-芳香族共聚酯按照CN100429256C中实施例B13-B21公开的方法自行制备得到，其中，可以根据目标产品的组成和分子量，相应地调整反应原料的种类，并且通过调整投料量和投料比分别控制产品的分子量以及产品中各重复单元的含量。
实施例1
将180g聚对苯二甲酸丁二醇酯(购自杜邦公司，牌号为Crastin SC164 NC010，下同)、20g对苯二甲酸丁二醇-丁二酸丁二醇共聚酯(重均分子量为100,000，其中，以丁二酸丁二醇重复单元和对苯二甲酸丁二醇重复单元的总摩尔数为基准，对苯二甲酸丁二醇重复单元的含量80摩尔％)和2g碳酸钙在搅拌的条件下混合，搅拌的速率为10rpm，时间为10min。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，螺杆扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为240℃、250℃、260℃、260℃、265℃、260℃，制得聚酯组合物A1。
对比例1
按照实施例1的方法制备聚酯组合物，所不同的是，不加入实施例1中使用的对苯二甲酸丁二醇-丁二酸丁二醇共聚酯，制得聚酯组合物D1。
对比例2
按照实施例1的方法制备聚酯组合物，所不同的是，聚对苯二甲酸丁二醇酯的用量是20g，对苯二甲酸丁二醇-丁二酸丁二醇共聚酯的用量是180g，制得聚酯组合物D2。
对比例3
按照实施例1的方法制备聚酯组合物，所不同的是，使用相同重量的聚丁二酸丁二醇酯(购自巴斯夫公司，牌号为1111HTA4)代替实施例1中使用的对苯二甲酸丁二醇-丁二酸丁二醇共聚酯，制得聚酯组合物D3。
对比例4
按照实施例1的方法制备聚酯组合物，所不同的是，使用相同重量的聚对苯二甲酸乙二醇酯(购自杜邦公司，牌号为FR530)代替实施例1中使用的对苯二甲酸丁二醇-丁二酸丁二醇共聚酯，制得聚酯组合物D4。
实施例2
将180g聚对苯二甲酸丁二醇酯(购自杜邦公司，牌号为Crastin SC164 NC010)、20g对苯二甲酸丁二醇-丁二酸丁二醇共聚酯(重均分子量为100,000，其中，以丁二酸丁二醇重复单元和对苯二甲酸丁二醇重复单元的总摩尔数为基准，对苯二甲酸丁二醇重复单元的含量60摩尔％)和2g碳酸钙在搅拌的条件下混合，搅拌的速率为10rpm，时间为10min。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，螺杆扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为240℃、250℃、260℃、260℃、265℃、260℃，制得聚酯组合物A2。
实施例3
将180g聚对苯二甲酸丁二醇酯(购自杜邦公司，牌号为Crastin SC164 NC010)、20g对苯二甲酸乙二醇-丁二酸乙二醇共聚酯(重均分子量为100,000，其中，以丁二酸乙二醇重复单元和对苯二甲酸乙二醇重复单元的总摩尔数为基准，对苯二甲酸乙二醇重复单元的含量80摩尔％)和2g碳酸钙在搅拌的条件下混合，搅拌的速率为10rpm，时间为10min。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，螺杆扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依 次为240℃、250℃、260℃、260℃、265℃、260℃，制得聚酯组合物A3。
实施例4
将180g聚对苯二甲酸丁二醇酯(购自杜邦公司，牌号为Crastin SC164 NC010)、20g对苯二甲酸丁二醇-己二酸丁二醇共聚酯(重均分子量为100,000，其中，以己二酸丁二醇重复单元和对苯二甲酸丁二醇重复单元的总摩尔数为基准，对苯二甲酸丁二醇重复单元的含量60摩尔％)和2g碳酸钙在搅拌的条件下混合，搅拌的速率为10rpm，时间为10min。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，螺杆扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为240℃、250℃、260℃、260℃、265℃、260℃，制得聚酯组合物A4。
实施例5
将160g聚对苯二甲酸丁二醇酯(购自杜邦公司，牌号为Crastin SC164 NC010)、40g对苯二甲酸丁二醇-己二酸丁二醇共聚酯(重均分子量为100,000，其中，以己二酸丁二醇重复单元和对苯二甲酸丁二醇重复单元的总摩尔数为基准，对苯二甲酸丁二醇重复单元的含量60摩尔％)和2g碳酸钙在搅拌的条件下混合，搅拌的速率为10rpm，时间为10min。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，螺杆扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为240℃、250℃、260℃、260℃、265℃、260℃，制得聚酯组合物A5。
实施例6
将160g聚对苯二甲酸丁二醇酯(购自杜邦公司，牌号为Crastin SC164 NC010)、40g对苯二甲酸丁二醇-己二酸丁二醇共聚酯(重均分子量为100,000，其中，以己二酸丁二醇重复单元和对苯二甲酸丁二醇重复单元的总摩尔数为基准，对苯二甲酸丁二醇重复单元的含量60摩尔％)和10g碳酸钙在搅拌的条件下混合，搅拌的速率为10rpm，时间为10min。将得 到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，螺杆扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为240℃、250℃、260℃、260℃、265℃、260℃，制得聚酯组合物A6。
实施例7
将160g聚对苯二甲酸丁二醇酯(购自杜邦公司，牌号为Crastin SC164 NC010)、40g对苯二甲酸丁二醇-己二酸丁二醇共聚酯(重均分子量为100,000，其中，以己二酸丁二醇重复单元和对苯二甲酸丁二醇重复单元的总摩尔数为基准，对苯二甲酸丁二醇重复单元的含量60摩尔％)和2g低密度聚乙烯(购自中石化燕山石化公司，牌号为LD607)在搅拌的条件下混合，搅拌的速率为10rpm，时间为10min。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，螺杆扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为240℃、250℃、260℃、260℃、265℃、260℃，制得聚酯组合物A7。
实施例8
将180g聚对苯二甲酸丁二醇酯(购自杜邦公司，牌号为Crastin SC164 NC010)、20g对苯二甲酸丁二醇-丁二酸丁二醇共聚酯(重均分子量为500,000，其中，以丁二酸丁二醇重复单元和对苯二甲酸丁二醇重复单元的总摩尔数为基准，对苯二甲酸丁二醇重复单元的含量80摩尔％)和2g碳酸钙在搅拌的条件下混合，搅拌的速率为10rpm，时间为10min。将得到的混合物通过双螺杆挤出机进行挤出造粒，螺杆的转速控制为10rpm，螺杆扭矩为20N*m，双螺杆挤出机中从进料口到挤出口各区段的温度依次为240℃、250℃、260℃、260℃、265℃、260℃，制得聚酯组合物A8。
实施例9
按照实施例1的方法制备聚酯组合物，所不同的是，不加入实施例1中使用的碳酸钙，制得聚酯组合物A9。
测试例
将实施例1-9和对比例1-4制得的聚酯组合物分别制成冲压样条，并将制成的冲压样条进行力学性能测试，如拉伸屈服强度(MPa)和断裂伸长率(％)，结果如下表1所示。
表1
  样条材质 拉伸屈服强度(MPa) 断裂伸长率(％)
测试例1 A1 54 320
测试例2 D1 58 8
测试例3 D2 25 520
测试例4 D3 50 12
测试例5 D4 51 10
测试例6 A2 53 370
测试例7 A3 45 230
测试例8 A4 53 380
测试例9 A5 48 520
测试例10 A6 50 450
测试例11 A7 51 480
测试例12 A8 55 310
测试例13 A9 52 320
通过将以上由实施例1-9和对比例1-4制备得到的聚酯组合物制成的冲压样条的力学性能测试结果相比较可以看出，本发明提供的聚酯组合物的断裂伸长率高达230％以上，韧性得到明显的改善，并且强度没有大幅的损失。并且，在该聚酯组合物的制备过程中，不需要额外加入相容剂。另外，本发明提供的聚酯组合物可以与PBT使用相同的设备进行加工，在其制备的过程中无需对加工设备进行额外的改造。因此，本发明 提供的聚酯组合物具有良好的工业应用前景。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (13)

  1. 聚酯组合物，含有
    (1)50-99重量％的聚对苯二甲酸丁二醇酯；和
    (2)1-50重量％的脂肪族-芳香族共聚酯，其中所述脂肪族-芳香族共聚酯为含有式(I)所示的重复单元A和式(II)所示的重复单元B的共聚物，
    Figure PCTCN2017107108-appb-100001
    其中，以所述脂肪族-芳香族共聚酯中的重复单元A和重复单元B的总摩尔数为基准，所述重复单元A的含量为1-60摩尔％，优选20-55摩尔％，更优选20-40摩尔％，所述重复单元B的含量为40-99摩尔％，优选45-80摩尔％，更优选60-80摩尔％；m为2-10的整数，n为2-8的整数，p为2-10的整数，优选m为2-6的整数，n为2-4的整数，p为2-6，优选2-4的整数；且m、n和p相同或不同；
    其中所述重量％以所述聚对苯二甲酸丁二醇酯和所述脂肪族-芳香族共聚酯的总重量为基准计算。
  2. 根据权利要求1所述的聚酯组合物，其特征在于，以所述聚对苯二甲酸丁二醇酯和所述脂肪族-芳香族共聚酯的总重量为基准，所述聚对苯二甲酸丁二醇酯的含量为70-95重量％，优选80-90重量％，所述脂肪族-芳香族共聚酯的含量为5-30重量％，优选10-20重量％。
  3. 根据权利要求1或2所述的聚酯组合物，其特征在于，所述脂肪族-芳香族共聚酯的重均分子量为50,000-900,000，优选100,000-500,000，该重均分子量根据GPC测得；优选，分子量分布为1.2-3，由GPC测得。
  4. 根据权利要求1-3中任一项所述的聚酯组合物，其特征在于，所述聚对苯二甲酸丁二醇酯的重均分子量为100,000-200,000，由GPC测得。
  5. 根据权利要求1-4中任意一项所述的聚酯组合物，其特征在于，所述聚酯组合物还含有成核剂；以所述聚酯组合物的总重量为基准，所述成核剂的含量为0.01-10重量％，优选为0.2-5重量％。
  6. 根据权利要求5所述的聚酯组合物，其特征在于，所述成核剂选自滑石粉、氧化钙、炭黑、碳酸钙、无机颜料、高岭土、羧酸金属盐、磷酸金属盐、二苄山梨醇及其衍生物、聚乙烯基环己烷、聚乙烯基环戊烷、低密度聚乙烯、超支化聚酰胺和乙烯-甲基丙烯酸离聚物中的一种或几种；优选为碳酸钙、低密度聚乙烯、二苄山梨醇及其衍生物和超支化聚酰胺中的一种或几种。
  7. 根据权利要求1-6中任意一项所述的聚酯组合物，其特征在于所述聚酯组合物还含有芥酸酰胺和/或白油。
  8. 根据权利要求1-7中任意一项所述的聚酯组合物，其特征在于，所述脂肪族-芳香族共聚酯为无规共聚物、交替共聚物、嵌段共聚物和接枝共聚物中的至少一种。
  9. 根据权利要求1-8中任意一项所述的聚酯组合物，其特征在于，聚酯组合物的断裂伸长率高达230％以上，根据GB/T 1040.2-2006方法测得。
  10. 制备根据权利要求1-9中任一项的聚酯组合物的方法，其特征在于，该方法包括：将包括聚对苯二甲酸丁二醇酯和脂肪族-芳香族共聚酯 在内的所有组分混合，并将得到的混合物进行挤出造粒，以得到聚酯组合物。
  11. 根据权利要求10所述的方法，其特征在于，所述混合在搅拌的条件下进行；并且，所述搅拌的速率为6-60rpm，所述搅拌的时间为2-30min；
    所述挤出造粒在双螺杆挤出机中进行；优选地，所述挤出造粒的条件包括：温度为230-300℃，螺杆转速为10-70rpm，扭矩为2-80N*m。
  12. 根据权利要求10或11所述的方法，其特征在于，所述混合的过程不加入相容剂。
  13. 增韧的复合材料，其由根据权利要求1-9中任一项的聚酯组合物制备。
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