CN112375342B - Functional master batch for polyester and preparation method thereof - Google Patents
Functional master batch for polyester and preparation method thereof Download PDFInfo
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- CN112375342B CN112375342B CN202011067342.7A CN202011067342A CN112375342B CN 112375342 B CN112375342 B CN 112375342B CN 202011067342 A CN202011067342 A CN 202011067342A CN 112375342 B CN112375342 B CN 112375342B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
Abstract
The application provides a functional master batch for polyester, which comprises a polyester carrier, functional material particles and 0.1-0.2 wt% of poly m-xylylene adipamide, wherein the functional material particles comprise polystyrene or polyethylene, polylactic acid, aerogel and polydimethylsiloxane. In addition, the application also provides a method for preparing the functional master batch. After the functional master batch is added, the influence on the viscosity of the original polyester is small, the stability of polyester parameters is favorably maintained, the using amount of anti-adhesion particles can be reduced, and the processing performance, the tensile strength, the light transmittance, the flame retardant property and the like of a polyester product are improved.
Description
Technical Field
The invention relates to a functional additive for preparing polyester products, which is a functional master batch prepared into a granular or sliced form. By adding the functional master batch of the invention into the polyester, the polyester can be used as all or part of raw materials for producing various polyester products, including but not limited to all or part of raw materials of surface layers or core layers of various polyester products such as optical products, packaging products, electronic devices and the like.
Background
Polyesters are a generic term for polymers obtained by polycondensation of polyhydric alcohols and polybasic acids. There are many types of polyesters, and PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PTT (polytrimethylene terephthalate), PCT (poly-1, 4-cyclohexanedimethanol terephthalate, and the like are well known to the public, and polyesters represented by PET in particular are widely used in various fields such as packaging, electronic and electronic appliances, optics, and the like because of their excellent heat resistance, mechanical strength, transparency, chemical resistance, and the like The field of manufacturing of large scale electronic devices is also becoming more important.
CN 104204089B discloses a polyester composition for film and a polyester film. The polyester composition for films is characterized by comprising the following components in a mass ratio of 1: 15-35: a polyester composition for a master batch, which contains 1.0 to 2.0 mass% of inorganic particles having an average particle diameter of 0.5 to 3.0 [ mu ] m and uses a polycondensation catalyst containing an aluminum compound and a phosphorus compound; and a polyester resin containing no inorganic particles. The inorganic particles are at least one inert inorganic particle selected from the group consisting of titanium dioxide, alumina, aluminosilicate, silica, calcium oxide, calcium carbonate, barium sulfate, talc, mica, kaolinite, and zeolite. In this prior art, inert inorganic particles are added in the polymerization step of the polyester for a masterbatch in order to improve the handling characteristics such as slip property, mobility, abrasion resistance, curling property, etc. These inorganic particles are slurried with a glycol to prevent flocculation, mechanically dispersed by a sand mill, a ball mill, ultrasonic waves, or the like, and then added with an alkali metal compound, an ammonium compound, or a phosphorus compound. The prior art considers that the affinity between the molecular chain of the polyester intermediate reactant and the inorganic particles can be improved due to the alkali metal compound, the ammonium compound and the phosphorus compound, so that the flocculation of the inorganic particles can be avoided, and the higher the concentration of the inorganic particles in the master batch is, the better the flocculation defect reduction effect of the inorganic particles is. However, the addition of the inorganic particles significantly reduces the light transmittance of the polyester film, which is very disadvantageous for producing high-quality polyester products.
CN 111032781 a discloses a polyester polymer composition, a polyester resin mother sheet and a polyester film using the polyester resin mother sheet. This prior art mentions that with the development of polyester films, higher surface flatness or less defective features than before are required. In order to solve the problem that agglomeration between added silica particles or between silica particles and a metal component added as a catalyst becomes a defect such as a fish eye at the time of surface formation of a huge projection or film formation, the prior art adopts a solution in which silica particles and a copolymer having a viscosity of 1000 to 20000cP are dispersed in ethylene glycol. This prior art lists many such copolymers and the range is quite broad. However, the uncontrolled transesterification of the copolymer with the addition of a large amount of other ingredients occurs during the polyester reaction, which changes the properties of the original polyester ingredients, especially the copolymer added to the polyester binds more strongly to the polyester ingredients, the copolymer is unbound to the silica, and the silica is still agglomerated after the addition, which affects the transparency and ductility of the final polyester product.
CN 103172990B proposes a high-transparency optical polyester film and a preparation method thereof, in the prior art, in order to avoid the influence of inorganic particles on the transmittance, the feeding of inorganic anti-blocking particles is completely eliminated, organic anti-blocking materials are used, although the effect is good, the price of the added organic anti-blocking particles is far higher than that of the inorganic particles, the cost is too high, and the high-transparency optical polyester film can only be applied to occasions with special high-quality requirements. On the other hand, various parameters determined by the application requirements of various polyester products are difficult to be prepared, and once the parameters of large-scale industrial production are determined, the stability of the parameters is generally required to be maintained, because the parameters are closely related to the final quality of the polyester products, and the unstable parameters require additional quality detection and comparison, thereby further increasing the cost. The organic anti-blocking material added into the polyester is easy to react with the polyester component, and may change the basic parameters of the viscosity of the polymerization product, which is very unfavorable for industrial production, and this also determines that the prior art is difficult to be popularized and applied in large scale.
Disclosure of Invention
The technical problem to be solved by the present application is to provide a functional masterbatch for polyester and a method for preparing the same, so as to reduce or avoid the aforementioned problems.
In order to solve the technical problem, the application provides a functional master batch for polyester, which comprises a polyester carrier, functional material particles and 0.1-0.2 wt% of poly m-xylylene adipamide, wherein the functional material particles comprise polystyrene or polyethylene, polylactic acid, aerogel and polydimethylsiloxane.
Preferably, the functional material particles respectively comprise the following components in parts by weight: 60-70 parts of aerogel, 10-15 parts of polylactic acid, 30-60 parts of polystyrene or polyethylene and 30-40 parts of polydimethylsiloxane.
Preferably, the content of the functional material particles in the functional master batch is 30 wt% to 40 wt%.
The invention also provides a preparation method of the functional master batch for the polyester, which comprises the following steps: uniformly mixing polystyrene or polyethylene, polylactic acid, aerogel and polydimethylsiloxane, extruding and granulating to obtain functional material particles; then adding the functional material particles in the form of particles or slices thereof and the poly m-xylylene adipamide into a polyester carrier; and finally preparing the functional master batch.
Preferably, the method further comprises: adding 60-70 parts by weight of aerogel particles, 10-15 parts by weight of polylactic acid particles and 10-15 parts by weight of polystyrene or polyethylene particles into 30-40 parts by weight of polydimethylsiloxane, and stirring at high speed to obtain a paste material; and uniformly mixing 20-45 parts by weight of polystyrene or polyethylene particles with the paste material, extruding and granulating to obtain functional material particles.
Preferably, the aerogel particles with the particle size of 0.5-10 μm are dried for 4 hours at 120 ℃; drying the polylactic acid particles with the particle size of less than 0.5mm for 4 hours at 110 ℃; drying the polystyrene or polyethylene particles with the particle size of less than 0.5mm for 4 hours at 110 ℃.
Preferably, the mixing and stirring speed of the dried particles put into the polydimethylsiloxane is 1000-1500 rpm.
Preferably, the functional material particles are selected to be added into the polyester carrier in an esterification stage, or after the esterification, or in a polycondensation stage, or after the polycondensation in the preparation process of the polyester carrier is completed; or uniformly mixing the carrier particles with the prepared polyester; and finally, extruding and granulating to obtain the functional master batch.
After the functional master batch is added, the influence on the viscosity of the original polyester is small, and the stability of polyester parameters is favorably maintained; the dosage of the anti-adhesion particles can be reduced; the processing property, tensile strength, light transmittance and flame retardant property of the polyester product are improved. In addition, the glossiness, the wear resistance, the high temperature resistance and the heat insulation performance of the polyester product can be improved.
Detailed Description
Detailed description of the drawings specific embodiments of the present application will now be described in detail for a more clear understanding of the technical features, objects and effects of the present application.
In view of the problems of the prior art, the present invention provides a functional additive for preparing a polyester article, which is a functional master batch prepared in the form of granules or chips, and a preparation method thereof. By adding the functional master batch of the invention into the polyester, the polyester can be used as all or part of raw materials for producing various polyester products, including but not limited to all or part of raw materials of surface layers or core layers of various polyester products such as optical products, packaging products, electronic devices and the like.
The polyester referred to in the present invention is a polyester comprising one or more selected from polybasic carboxylic acids containing dibasic acids and their ester-forming derivatives, and one or more selected from polyhydric alcohols containing dibasic alcohols; or a polyester formed from a hydroxycarboxylic acid or an ester-forming derivative thereof; or a polyester formed from a cyclic ester. The polyester can be produced by a conventionally known method. For example, taking the preparation of PET as an example, it can be obtained by: a method of performing polycondensation after esterification of terephthalic acid and ethylene glycol; or a method in which an alkyl ester of terephthalic acid such as dimethyl terephthalate is subjected to a transesterification reaction with ethylene glycol and then subjected to polycondensation.
In the process of producing the polyester product, the functional master batch provided by the invention can be added into common polyester granules in the form of granules or chips so as to enable the produced polyester product to have the functional characteristics of the functional master batch provided by the invention. For example, 70 to 99 wt% of polyester without other components and 1 to 30 wt% of the functional master batch of the present invention may be subjected to melt blending, and then a polyester film is obtained through stretching or other processes, or a surface layer structure of a heat shrinkable film, a release film or an optical film is obtained through a multilayer co-extrusion process, or a polyester container is produced through a blow molding or other processes, or a polyester structural component is produced through an injection molding, pultrusion or other processes, and the like.
The functional master batch for polyester comprises a polyester carrier, polystyrene or polyethylene, polylactic acid, aerogel and polydimethylsiloxane. When the functional master batch is suitable for being added into the main polyester PET, for example, the polyester carrier of the functional master batch can be correspondingly selected to be the PET, so that the compatibility of the functional master batch and the main polyester PET is better, and the performance of the original polyester is prevented from being changed by unnecessary ester exchange. Likewise, when the functional masterbatch is suitable for addition to other host polyesters, such as PBT, PTT, PCT, or PETG, the polyester carrier in the functional masterbatch is preferably the same as the host polyester. Of course, under the conditions of similar properties and relatively good compatibility, the polyester carrier and the main polyester in the functional master batch can also be different, but the control of the product quality is possibly difficult. Silica aerogel is commonly called as 'blue smoke', is low-density silica aerogel with porous, disordered and nano-scale continuous network structure, has a larger specific surface area than common silica, and is more difficult to disperse than common silica by using phosphate coupling agents and silane coupling agents (such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane and the like) in the prior art. Because of its very low density, it floats easily and cannot be dispersed into the polyester. The porous structure of the aerogel can generate strong bonding force with polylactic acid, polypropylene ethylene or polyethylene through polydimethylsiloxane, the density of the aerogel is increased, and the aerogel can be sunk into the polyester.
The polyester carrier in the functional masterbatch of the present invention may be formed by, for example, polycondensation of a dibasic acid and a glycol. For example, the dibasic acid component thereof, including, but not limited to, terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, 3, 4 '-diphenylether dicarboxylic acid, hexahydrophthalic acid, 2, 7-naphthalenedicarboxylic acid, phthalic acid, 4' -methylenebisbenzoic acid, oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 3-methyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1, 11-undecanedicarboxylic acid, 1, 10-decanedicarboxylic acid, undecanedicarboxylic acid, 1, 12-dodecanedicarboxylic acid, hexadecanedioic acid, docosanedicarboxylic acid, lignoceric acid, dimer acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1-cyclohexanediacetic acid, fumaric acid, maleic acid, and hexahydrophthalic acid. Further, these may be used alone or in combination of two or more.
For example, the diol component includes, but is not limited to, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 14-tetradecanediol, 1, 16-hexadecanediol, dimer diol, diethylene glycol, triethylene glycol, poly (ethylene ether) glycol, poly (butylene ether) glycol, branched diols, hexanediol, or combinations or derivatives thereof, 1, 4-cyclohexanedimethanol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-2, 4-pentanediol, neopentyl glycol, 2-methyl-1, 4-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2, 5-ethyl-1, 3-hexanediol, 2-diethyl-1, 3-propanediol, 1, 3-hexanediol. Further, these may be used alone or in combination of two or more.
The polyester carrier in the functional masterbatch of the present invention may be formed of hydroxycarboxylic acids and their ester-forming derivatives, or may be formed of cyclic esters.
For example, the hydroxycarboxylic acid component includes, but is not limited to: lactic acid, citric acid, malic acid, tartaric acid, glycolic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid and the like. The ester-forming derivatives of hydroxycarboxylic acids include, but are not limited to: dimethyl terephthalate, dimethyl isophthalate, dimethyl 2, 6-naphthalenedicarboxylate, dimethyl 3, 4 '-diphenylether dicarboxylate, dimethyl hexahydrophthalate, dimethyl 2, 7-naphthalenedicarboxylate, dimethyl phthalate, dimethyl 4, 4' -methylenebisbenzoate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl azelate, dimethyl 1, 3-cyclohexanedicarboxylate and dimethyl 5-sulfoisophthalate. Further, these may be used alone or in combination of two or more. For example, cyclic esters include, but are not limited to: epsilon-caprolactone, beta-propiolactone, beta-methyl-beta-propiolactone, delta-valerolactone, glycolide, lactide, and the like. Further, these may be used alone or in combination of two or more.
The polyester carrier used in the present invention is preferably polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly-1, 4-cyclohexanedimethanol terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate, and a copolymer thereof, and particularly preferably polyethylene terephthalate (PET) and a copolymer thereof.
The polyester support of the present invention is preferably produced industrially by a polycondensation method in which, for example, PET is esterified or transesterified with terephthalic acid or dimethyl terephthalate and ethylene glycol to produce bishydroxyethyl terephthalate, and the bishydroxyethyl terephthalate is polycondensed at high temperature under vacuum using a catalyst. In one embodiment, esterification can be carried out from terephthalic acid, ethylene glycol, cyclohexanedimethanol, a catalyst and a heat stabilizer; or esterification is carried out by taking terephthalic acid, ethylene glycol, isophthalic acid, a catalyst and a heat stabilizer as raw materials. In another embodiment, the catalyst is any one of Ti/Si series non-heavy metal catalyst and antimony trioxide, and the addition amount of the catalyst is 0.01-0.09% of the mass of the polyester. In another specific embodiment, the heat stabilizer is a phosphoric acid compound, and the addition amount of the phosphoric acid compound is 0.0003-0.030% of the mass of the polyester; the phosphoric acid compound comprises any one of phosphoric acid, phosphorous acid, polyphosphoric acid, trimethyl phosphate, triphenyl phosphate and triethyl phosphate. The preparation of the polyester support of another embodiment is as follows: adding 5.0kg of terephthalic acid, 2.2kg of ethylene glycol and 1.10g of germanium dioxide into a 20L general polymerization reaction kettle, carrying out esterification reaction at 230-265 ℃ and 0.2-0.3 Mpa (gauge pressure), releasing pressure to normal pressure when the water yield reaches 1200ml, adding 1.025g of triphenyl phosphate, stirring for 10 minutes at normal pressure, raising the temperature and reducing the pressure to 280 ℃ and below 100Pa, and after 1-3 hours of reaction, extruding, granulating and drying to obtain the polyester carrier.
In the functional masterbatch for polyester of the present invention, the components except the polyester carrier may be uniformly mixed, and then extruded and granulated by using equipment such as an extruder to obtain the functional material particles, and then the functional material particles are added to the polyester carrier in the form of particles or chips thereof, and finally the functional masterbatch of the present invention is prepared. That is, the functional masterbatch for polyester of the present invention comprises a polyester carrier and functional material particles comprising polystyrene or polyethylene, polylactic acid, aerogel and polydimethylsiloxane. Preferably, the functional material particles comprise the following components in parts by weight: 60-70 parts of aerogel, 10-15 parts of polylactic acid, 30-60 parts of polystyrene or polyethylene and 30-40 parts of polydimethylsiloxane. The functional material particles can be used as independent additives to be directly added into polyester to produce polyester products, the properties of the independent functional material particles are soft, and in order to facilitate long-term storage and avoid pollution, the functional material particles are preferably added into a polyester carrier at the content of 30 wt% -40 wt% to prepare a functional master batch, namely, the content of the functional material particles in the functional master batch is 30 wt% -40 wt%. For example, after the polyester carrier particles are prepared, 100 parts by weight of polyester carrier chips are taken, 60 parts by weight of functional material particles are added, the mixture is uniformly mixed, and then the mixture is melted, extruded and cut into particles through an extruder, so that the functional master batch of the invention can be obtained.
In addition, because the content of the functional material particles in the prepared functional master batch is up to 30-40 wt%, in order to avoid the oxidation and decomposition of the effective components during storage, in the process of preparing the functional master batch, the functional material particles are preferably added into a polyester carrier at the content of 30-40 wt%, and 0.1-0.5 wt% of poly m-xylylene adipamide is simultaneously added.
When the functional material particles are added to the polyester carrier, the polylactic acid is easily decomposed into water and carbon dioxide at high temperature, thereby being separated from the aerogel. The silicon atoms of the aerogel are combined with the silicon atoms of the polydimethylsiloxane, the macromolecules at the other end of the polydimethylsiloxane can be combined with the alkane of the polyester, and the aerogel can still be kept in the polyester through the polydimethylsiloxane even if the affinity of polylactic acid is lost. And carbon dioxide generated by the decomposed polylactic acid can form bubbles to bring other solid inorganic particles in the polyester to the surface layer of the product, for example, a metal salt antioxidant, a catalyst and the like can be brought to the surface layer part of the polyester, so that a convex-concave structure can be formed on the surface of the polyester, the anti-blocking effect is realized, the adding amount of the inorganic anti-blocking particles can be reduced, and the light transmittance of the polyester is improved. For example, it is detected that the anti-blocking effect of the polyester film is not obviously changed and the light transmittance of the polyester film can be greatly improved under the condition of reducing the dosage of the anti-blocking particles by 20 to 30 percent.
In one embodiment of the present invention, 60 to 70 parts by weight of aerogel particles having a particle size of 0.5 to 10 μm can be preferably dried at 120 ℃ for 4 hours; drying 10-15 parts by weight of polylactic acid particles with the particle size of less than 0.5mm at 110 ℃ for 4 hours; drying 10-15 parts by weight of polystyrene or polyethylene particles with the particle size of less than 0.5mm at 110 ℃ for 4 hours. And putting the dried particles into 30-40 parts by weight of liquid polydimethylsiloxane at normal temperature, and stirring at the speed of 1000-1500rpm for 2 hours to obtain a paste material. 20-45 parts by weight of polystyrene or polyethylene particles (which can be dried only in a purchased particle form without being crushed) dried at 110 ℃ for 4 hours are put into a mixing area of an extruder together with the paste material, and the functional material particles are obtained by melt extrusion and granulation after uniform mixing.
Polydimethylsiloxane is insoluble in water, has poor affinity with common inorganic particles, can be dispersed by shearing force of high-speed stirring, and is not suitable for being directly added into polyester. The silicon atoms of the polydimethylsiloxane can form firm molecular combination with the silicon atoms of the aerogel, the binding force is strong, and the polydimethylsiloxane and the aerogel cannot be separated by applying high-speed stirring. The polymer at the other end of the polydimethylsiloxane can be combined with the alkane of the polyester, and the binding force is strong. Not only has good dispersion effect, but also can not be separated from the combination to generate agglomeration phenomenon due to the molecular combination. While the ordinary silicon dioxide has smooth surface and insufficient bonding force with the existing coupling agent, the ordinary silicon dioxide can be separated from the coupling agent when the stirring force is too large during dispersion, and the ordinary silicon dioxide can still agglomerate when added into polyester.
The functional material particles can be selectively put into the polyester carrier in the preparation process of the polyester carrier, for example, the functional material particles can be put into the polyester carrier in the esterification stage in the preparation process of the polyester carrier, or after the esterification, or in the polycondensation stage, or after the polycondensation is completed, and finally, the functional master batch for the polyester can be obtained by extrusion granulation. Alternatively, the prepared polyester carrier particles and the functional material particles or the slices thereof can be uniformly mixed, and finally extruded and granulated to obtain the functional master batch for polyester.
Through detection, after the functional master batch is added, the influence on the viscosity of the original polyester is small, and the stability of polyester parameters is favorably maintained. In addition, the glossiness, the wear resistance, the high temperature resistance and the heat insulation performance of the polyester product are all improved by 10 to 20 percent.
Examples
The meanings of the abbreviations in the following examples are as follows:
terephthalic acid: PTA ethylene glycol: EG polystyrene: PS (polystyrene) with high sensitivity
Polyethylene: PE polylactic acid: PLA polydimethylsiloxane: PDMS
The following examples use PET or PETG as the polyester carrier, aerogel and ordinary SiO2And (6) carrying out comparison.
See table below for the ingredients of the examples and comparative examples.
The functional master batches prepared in examples 1 to 3 and comparative examples 1 to 3 were mixed according to SiO2The amount of (B) was 3.0% of the total mass, and the resulting melt-blended product was drawn into a 60 μm film by melt-blending with ordinary PET, and the properties were measured as follows.
It should be appreciated by those skilled in the art that while the present application is described in terms of several embodiments, not every embodiment includes only a single embodiment. The description is thus given for clearness of understanding only, and it is to be understood that all matters in the embodiments are to be interpreted as including all technical equivalents which are encompassed by the claims and are to be interpreted as combined with each other in a different embodiment so as to cover the scope of the present application.
The above description is only illustrative of the present invention and is not intended to limit the scope of the present invention. Any equivalent alterations, modifications and combinations that may be made by those skilled in the art without departing from the spirit and principles of this application shall fall within the scope of this application.
Claims (4)
1. The functional master batch for the polyester is characterized by comprising a polyester carrier, functional material particles and 0.1-0.2 wt% of poly m-xylylene adipamide, wherein the functional material particles comprise the following components in parts by weight: 60-70 parts of silicon dioxide aerogel, 10-15 parts of polylactic acid, 30-60 parts of polystyrene or polyethylene and 30-40 parts of polydimethylsiloxane; the content of the functional material particles in the functional master batch is 30-40 wt%.
2. A preparation method of a functional master batch for polyester comprises the following steps: adding 60-70 parts by weight of silica aerogel particles, 10-15 parts by weight of polylactic acid particles and 10-15 parts by weight of polystyrene or polyethylene particles into 30-40 parts by weight of polydimethylsiloxane, and stirring at high speed to obtain a paste material; uniformly mixing 20-45 parts by weight of polystyrene or polyethylene particles with the paste material, extruding and granulating to obtain functional material particles; then adding the functional material particles in the form of particles or slices thereof and the poly m-xylylene adipamide into a polyester carrier; finally, preparing and obtaining functional master batch; wherein the content of the functional material particles in the functional master batch is 30-40 wt%, and the content of the poly m-xylylene adipamide is 0.1-0.2 wt%.
3. The method of claim 2, wherein the silica aerogel particles having a particle size of 0.5 to 10 μm are dried at 120 ℃ for 4 hours; drying the polylactic acid particles with the particle size of less than 0.5mm for 4 hours at 110 ℃; drying the polystyrene or polyethylene particles with the particle size of less than 0.5mm for 4 hours at 110 ℃.
4. The method of claim 3, wherein the mixing and stirring speed of the dried particles into the polydimethylsiloxane is 1000-1500 rpm.
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| CN101098916A (en) * | 2005-01-13 | 2008-01-02 | 金文申有限公司 | Composite materials containing carbon nanoparticles |
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| CN106313827A (en) * | 2015-07-01 | 2017-01-11 | 江苏裕兴薄膜科技股份有限公司 | Impact-resistant modified polyester film and preparation method thereof |
| KR20200108594A (en) * | 2019-03-11 | 2020-09-21 | 한양대학교 산학협력단 | Composition for Radiative Cooling Film and Radiative Cooling film Prepared from Same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101098916A (en) * | 2005-01-13 | 2008-01-02 | 金文申有限公司 | Composite materials containing carbon nanoparticles |
| CN106313827A (en) * | 2015-07-01 | 2017-01-11 | 江苏裕兴薄膜科技股份有限公司 | Impact-resistant modified polyester film and preparation method thereof |
| CN105479880A (en) * | 2015-12-06 | 2016-04-13 | 安徽国风塑业股份有限公司 | High breakdown-resistant, flame retardant and biaxially oriented polyester film and preparation method thereof |
| KR20200108594A (en) * | 2019-03-11 | 2020-09-21 | 한양대학교 산학협력단 | Composition for Radiative Cooling Film and Radiative Cooling film Prepared from Same |
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