CN110698821B - Multi-oxygen-containing functional polyester resin, and preparation method and application thereof - Google Patents
Multi-oxygen-containing functional polyester resin, and preparation method and application thereof Download PDFInfo
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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Abstract
The invention relates to the technical field of modified polyester resin, in particular to a multi-oxygen-containing functional polyester resin, a preparation method and application thereof. The preparation method of the poly-oxygen-containing functional polyester resin comprises the following steps: (R1) placing polyester resin at a lower air inlet of a PECVD reaction cavity, vacuumizing the PECVD reaction cavity, continuously introducing oxygen, and controlling the gas pressure of the PECVD reaction cavity to be 4-10 Pa; (R2), exciting oxygen into plasma under the action of an excitation source and reacting with the polyester resin to obtain the oxygen-containing functional polyester resin. The preparation method of polyester resin with multiple oxygen-containing functional groups comprises the steps of reacting oxygen excitation layer plasma with the polyester resin by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method to increase active oxygen-containing functional groups of the polyester resin; the preparation method has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
Description
Technical Field
The invention relates to the technical field of modified polyester resin, in particular to a multi-oxygen-containing functional polyester resin, a preparation method and application thereof.
Background
Polyester, a general term for polymers obtained by polycondensation of polyhydric alcohols and polybasic acids, mainly refers to polyethylene terephthalate (PET), and conventionally also includes linear thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylate, and is a kind of engineering plastics with excellent performance and wide application, and can be made into polyester fibers and polyester films.
In order to further improve the mechanical property, flame retardant property and high temperature resistance of polyester resin to adapt to application occasions with higher requirements and wider range, the traditional method is to mix inorganic filler into the polyester resin to obtain composite materials or mix polymer materials such as nylon and the like to obtain alloy materials, because of the problem of poor compatibility among the materials, a compatilizer is often added to improve the compatibility of the materials, but the existing compatilizer has higher molecular weight, the processing fluidity of the materials is easily reduced after the compatilizer is added, and the raw material cost of the compatilizer with lower molecular weight and good compatibility is high, thus being not beneficial to the economic benefit of enterprises.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, one of the purposes of the invention is to provide a preparation method of polyester resin with multiple oxygen-containing functional groups, which utilizes a Plasma Enhanced Chemical Vapor Deposition (PECVD) method to react oxygen excitation layer plasma with the polyester resin so as to increase the active oxygen-containing functional groups such as hydroxyl, carboxyl and the like in the polyester resin; the preparation method has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
The second purpose of the invention is to provide a multi-oxygen-containing functional polyester resin, which has increased active oxygen-containing functional groups such as hydroxyl, carboxyl and the like, so that the surface is changed from non-polar and difficult-to-stick to have certain polarity, easy-to-stick property and affinity, and the compatibility with inorganic fillers or high polymer materials such as nylon and the like is improved.
The invention also aims to provide the application of the poly-oxygen-containing functional polyester resin, which is applied to the polyester composite material, and can improve various properties of the polyester composite by adding the inorganic filler under the condition of not using the traditional compatilizer, and the strength of the polyester composite is not reduced.
The purpose of the invention is realized by the following technical scheme: a preparation method of polyester resin with multiple oxygen-containing functional groups comprises the following steps:
(R1) pretreatment before reaction: placing polyester resin at a lower air inlet of a PECVD reaction cavity, vacuumizing the PECVD reaction cavity, continuously introducing oxygen, and controlling the air pressure of the PECVD reaction cavity to be 4-10 Pa;
(R2), plasma enhanced chemical vapor deposition: exciting oxygen into plasma under the action of an excitation source and reacting with polyester resin to obtain the oxygen-containing functional polyester resin.
The preparation method of the polyester resin with multiple oxygen-containing functional groups utilizes a Plasma Enhanced Chemical Vapor Deposition (PECVD) method to excite the plasma of an oxygen excitation layer and then react with the polyester resin, so that the polyester resin is increased with active oxygen-containing functional groups such as hydroxyl, carboxyl and the like; the preparation method has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production. In the step (R1), the polyester resin is placed in the lower tuyere of the PECVD reaction cavity, oxygen enters the PECVD reaction cavity through the upper tuyere of the PECVD reaction cavity, and then is excited by the excitation source to generate plasma, and is pushed to the lower tuyere of the PECVD reaction cavity to react with the polyester resin by virtue of the continuously introduced oxygen, so as to facilitate the generation of glow discharge or high-frequency discharge under the action of the excitation source in the step (R2) to generate cathode sputtering, and the temperature of the PECVD reaction cavity is raised by utilizing the glow discharge or high-frequency discharge to further raise the temperature of the polyester resin, thereby improving the surface activity of the polyester resin; introducing oxygen after vacuumizing, creating a low-pressure environment and maintaining a stable vacuum degree, exciting the oxygen into plasma under the action of an excitation source in the step (R2), and enabling the plasma to contact the heated polyester resin to perform a plasma chemical reaction so that the polyester resin obtains active oxygen-containing functional groups such as hydroxyl, carboxyl and the like, thereby improving the compatibility of the poly-oxygen-containing functional polyester resin with other raw materials; the gas pressure of the PECVD reaction cavity is controlled to be 4-10Pa, and the plasma glow can be ensured. Further, the polyester resin is at least one of polybutylene terephthalate, polyethylene terephthalate and poly 1, 4-cyclohexanedimethanol terephthalate; the intrinsic viscosity of the polybutylene terephthalate is 0.7-1.2dL/g, and preferably, the intrinsic viscosity of the polybutylene terephthalate is 0.8 dL/g; the intrinsic viscosity of the polyethylene terephthalate is 0.7-1.2dL/g, and preferably, the intrinsic viscosity of the polyethylene terephthalate is 0.7 dL/g; the intrinsic viscosity of the poly (1, 4-cyclohexanedimethanol terephthalate) is 0.7-1.2dL/g, and preferably, the intrinsic viscosity of the poly (1, 4-cyclohexanedimethanol terephthalate) is 0.7 dL/g.
Preferably, in the step (R2), the excitation source is radio frequency, direct current high voltage, pulse or microwave, the output power of the excitation source is 200-300W, and the reflection power of the excitation source is 0-30W; the reaction time is 1-2 h.
The excitation source is used for promoting oxygen to be excited into plasma and the cathode to generate glow discharge or high-frequency discharge, and more preferably, the excitation source is radio frequency, and specifically, an inductively coupled plasma radio frequency power supply is used for generating the excitation source. The output power of the excitation source is controlled to be 200-300W, and the reaction process is fully absorbed, so that the reflection power of the excitation source is only 0-30W, and the effective power is high; in addition, the output power of the excitation source is controlled to be 200-300W, the activity of the plasma is stronger under the power condition, and the treatment efficiency is higher; if the output power of the excitation source is too high, the molecular structure of the polyester resin is easily damaged and degraded due to too large energy absorption of the polyester resin. The reaction time is controlled to be 1-2h, so that the polyester resin is fully modified.
Preferably, the polyester resin is polyester powder having a particle size of 6.5 to 10 μm.
The particle size of the polyester resin is controlled to be 6.5-10 mu m, so that the reaction area of the polyester resin and oxygen can be increased, more oxygen-containing active groups can be obtained, and the compatibility of the polyester resin with multi-oxygen-containing functional groups and other raw materials can be improved.
Preferably, the step (R2) further includes: after the plasma reacts with the polyester resin, the PECVD reaction cavity stops the action of the excitation source and the introduction of oxygen, and the PECVD reaction cavity is cooled to normal temperature under the condition of the environmental pressure of 4-10 Pa.
By adopting the technical scheme, the multi-oxygen-containing functional group polyester resin is cooled to normal temperature, the phenomenon that the multi-oxygen-containing functional group polyester resin is oxidized to introduce impurities due to the fact that air is introduced into the polyester resin at normal pressure under the high-temperature state after the polyester resin is heated by glow discharge is avoided, and the stability of the multi-oxygen-containing functional group polyester resin is greatly improved. Further, the normal pressure can be recovered after the temperature is reduced to the normal temperature.
The second purpose of the invention is realized by the following technical scheme: the polyester resin containing multiple oxygen functional groups is prepared by the preparation method of the polyester resin containing multiple oxygen functional groups.
The third purpose of the invention is realized by the following technical scheme: the application of the multifunctional oxygen-containing polyester resin is that the multifunctional oxygen-containing polyester resin is applied to a polyester composite material.
Preferably, the polyester composite material comprises the following raw materials in parts by weight:
the polyester composite material provided by the invention adopts the multi-oxygen-containing functional polyester resin as the main resin, and the flame retardant, the flame-retardant synergist, the glass fiber and the antioxidant are added, so that the flame retardant effect, the mechanical strength and the aging resistance of the polyester composite material are improved, and the problem of the compatibility of the multi-oxygen-containing functional polyester resin with the flame retardant, the flame-retardant synergist, the glass fiber and the antioxidant, which causes easy embrittlement, and the reduction of the mechanical property of the polyester composite material is avoided. The other auxiliary agent is toner.
Further, the antioxidant is a hydrolysis-resistant antioxidant, more preferably, the antioxidant is formed by mixing a hindered phenol main antioxidant and a thioether auxiliary antioxidant in a weight ratio of 1:2-5, the hindered phenol main antioxidant and the thioether auxiliary antioxidant act synergistically, and in the aging process of the polyester composite material, peroxide radicals are effectively captured to terminate the oxidation process, so that the antioxidant effect is achieved, the antioxidant effect is good at high temperature, and the antioxidant is not easy to hydrolyze in a high-humidity state; compared with amine antioxidants, the antioxidant is not easy to separate out under the conditions of high temperature and high humidity, so that the lasting anti-aging effect is kept; compared with the synergy of the hindered phenol main antioxidant and the phosphite ester auxiliary antioxidant, the hindered phenol main antioxidant and the thioether auxiliary antioxidant are mixed according to the weight ratio of 1:2-5, although the antioxidant effect is not better than the synergistic antioxidant effect of the hindered phenol main antioxidant and the phosphite ester auxiliary antioxidant in a short time, the phosphite ester auxiliary antioxidant is hydrolyzed, but the antioxidant is not easily hydrolyzed, so that the antioxidant can maintain the anti-aging effect for a long time, and is more favorable for playing the antioxidant effect under the conditions of high temperature and high humidity. The hindered phenol main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) according to the weight ratio of 5: 1-3, mixing; the thioether auxiliary antioxidant is dilauryl thiodipropionate and 2, 4-di (n-octyl thiomethylene) -6-methylphenol according to the weight ratio of 1-3: 1 are mixed.
Further, the flame retardant is at least one of brominated polystyrene, brominated epoxy, brominated polycarbonate and brominated triazine; the flame-retardant synergist is an organic silicon flame retardant with the relative molecular weight of 20000-38000. The flame retardant and the flame retardant synergist act synergistically to prevent the probability of forming carbon channels by the polyester resin, so that the CTI value of the polyester composite material is improved. The organic silicon flame retardant is at least one of polydimethylsiloxane, polydiethylsiloxane, polymethylsiloxane and polymethylphenylsiloxane, and the flame retardant system does not contain nitrogen element series synergist which is easy to precipitate at high temperature and high humidity, so that the char forming rate of the polyester composite material during combustion can be effectively improved, and the flame retardant effect is improved. The relative molecular weight control of the organosilicon flame retardant is 20000-38000, a high molecular gradient material of an organosilicon flame retardant enrichment layer is formed on the surface of the polyester composite material, and the polyester composite material generates an inorganic oxygen-insulating and heat-insulating protective layer which is peculiar to polysiloxane and contains Si-O bonds and/or Si-C bonds during combustion, so that the escape of combustion decomposition products is prevented, no precipitate is formed on the surface of the polyester composite material, the thermal decomposition of polyester resin is inhibited, and the flame retardant effect is achieved.
Preferably, the glass fiber is high modulus glass fiber or flat glass fiber, and the chopped length of the glass fiber is 2.0-4.5 mm.
The glass fiber has lower warping degree and better dimensional stability, is beneficial to improving the fiber content and the mechanical property, enables the polyester composite material to have higher impact strength, and can reduce the warping degree of the polyester composite material. Further, the elastic modulus of the high-modulus glass fiber is 93.0-95.0 GPa. The chopped length of the glass fiber is controlled to be 2.0-4.5mm, after processing, the reserved length of the glass fiber tends to the critical optimal length, and the mechanical properties of the polyester composite material, such as flexural modulus, tensile strength, compressive strength, flexural strength, rigidity and the like, are further enhanced.
Preferably, the preparation method of the polyester composite material comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), premixing the polyester resin with the multi-oxygen-containing functional group and the diffusion oil in a high-speed mixer for 1-3min, then blending with other raw materials for 1-3min, discharging, and extruding and granulating through a double-screw extruder under the condition of screw combination with certain strength shearing to obtain the polyester composite material.
The preparation method of the polyester composite material is simple to operate, convenient to control, high in production efficiency and low in production cost, and can be used for large-scale production. In the step (S2), the multi-oxygen-containing functional group polyester resin is premixed with the diffusion oil in a high-speed mixer and then blended with other raw materials, which is beneficial to uniformity and stability of the material in the extrusion process. The diffusion oil can uniformly disperse insoluble inorganic/organic solids such as glass fibers and toner, and can prevent the solids from settling and coagulating and improve the processing fluidity.
Further, the processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 190 ℃ at 170-. According to the invention, the temperature of each zone in the double-screw extruder is controlled, so that the prepared polyester composite material has excellent mechanical property, and is free from yellowing and foaming, smooth in surface and high in glossiness.
Preferably, the screw assembly comprises the following components in sequence from the machine head to the machine tail: 32/32, 48/24, 48/48, 48/48, 48/48, 64/46, 64/64, 64/64, ZME12/24, ZME12/24, 48/48, 48/48, ZME12/24, 48/48, K45 °/5/48, K45 °/5/48, 64/64, 64/64, 64/64, 48/48, 64/64, 64/64, 32/16L, K45 °/5/48, K45 °/5/48, K45 °/5/48, K45 °/5/48, 48/48, K45 °/5/48, K45 °/5/48, K30 °/7/64, 48/48, 48/48, 48/48, 48/48, 64/64, 64/64, 48/48A; the length of the screw combination is 1888-2000 mm.
When the specific screw combination is applied to the preparation of the polyester composite material, the good distribution and dispersion effects can be achieved, the retention length of the glass fiber can be ensured, and if the shearing of the screw combination is too strong, although the material is well dispersed, the retention length of the glass fiber is lower, so that the polyester is not beneficial to be reinforced; if the shearing force of the screw combination is too weak, the material dispersion effect is poor, the material performance is also reduced, and more seriously, the glass fiber is sheared continuously to cause material pulling and easy strip breaking. By adopting the specific screw combination, the retention length of the treated glass fiber in the polyester composite material can reach 0.6-1.5mm, the retention length of the glass fiber is the critical proper length of the glass fiber, and the distribution of the glass fiber length is narrow.
The invention has the beneficial effects that: according to the preparation method of the polyester resin with multiple oxygen-containing functional groups, plasma of an oxygen excitation layer is reacted with the polyester resin by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, so that the polyester resin is increased with active oxygen-containing functional groups such as hydroxyl, carboxyl and the like; the preparation method has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
The multi-oxygen-containing functional polyester resin has increased active oxygen-containing functional groups such as hydroxyl, carboxyl and the like, so that the surface is changed from non-polar and difficult-to-stick to have certain polarity, easy-to-stick property and affinity, and the compatibility of the multi-oxygen-containing functional polyester resin with inorganic fillers or high polymer materials such as nylon and the like is improved.
The application of the poly-oxygen-containing functional polyester resin is applied to the polyester composite material, and the inorganic filler is added under the condition of not using the traditional compatilizer, so that various properties of the polyester composite can be improved, and the strength of the polyester composite is not reduced.
Drawings
FIG. 1 is a schematic structural view of a screw assembly according to embodiment 1 of the present invention.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention.
Example 1
A preparation method of polyester resin with multiple oxygen-containing functional groups comprises the following steps:
(R1) pretreatment before reaction: placing polyester resin at a lower air inlet of a PECVD reaction cavity, vacuumizing the PECVD reaction cavity, continuously introducing oxygen, and controlling the air pressure of the PECVD reaction cavity to be 7 Pa;
(R2), plasma enhanced chemical vapor deposition: exciting oxygen into plasma under the action of an excitation source and reacting with polyester resin to obtain the oxygen-containing functional polyester resin.
The polyester resin is polybutylene terephthalate; the intrinsic viscosity of the polybutylene terephthalate is 0.8 dL/g.
In the step (R2), the excitation source is radio frequency, the output power of the excitation source is 250W, and the reflection power of the excitation source is 15W; the reaction time was 1.5 h.
The polyester resin is polyester powder with the particle size of 8 mu m.
The step (R2) further comprises: after the plasma reacts with the polyester resin, the PECVD reaction cavity stops the action of the excitation source and the introduction of oxygen, and the PECVD reaction cavity is cooled to normal temperature under the condition of the ambient pressure of 7 Pa.
The polyester resin containing multiple oxygen functional groups is prepared by the preparation method of the polyester resin containing multiple oxygen functional groups.
The application of the multifunctional oxygen-containing polyester resin is that the multifunctional oxygen-containing polyester resin is applied to a polyester composite material.
The polyester composite material comprises the following raw materials in parts by weight:
the antioxidant is formed by mixing a hindered phenol main antioxidant and a thioether auxiliary antioxidant according to the weight ratio of 1: 4; the hindered phenol main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) according to the weight ratio of 5: 2, mixing; the thioether auxiliary antioxidant is dilauryl thiodipropionate and 2, 4-di (n-octyl thiomethylene) -6-methylphenol according to the weight ratio of 2: 1 are mixed.
The flame retardant is brominated polystyrene; the flame-retardant synergist is an organic silicon flame retardant with the relative molecular weight of 30000. The organic silicon flame retardant is polydimethylsiloxane.
The glass fiber is high-modulus glass fiber, and the chopped length of the glass fiber is 3 mm. The elastic modulus of the high-modulus glass fiber is 94.0 GPa.
The preparation method of the polyester composite material comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), premixing the polyester resin with the multi-oxygen-containing functional group and the diffusion oil in a high-speed mixer for 2min, then blending the premixed polyester resin with other raw materials for 2min, discharging, and carrying out extrusion granulation by a double-screw extruder under the condition of screw combination with certain strength shearing to obtain the polyester composite material.
The processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 180 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ of head temperature and 360r/min of screw rotation speed.
As shown in fig. 1, the screw assembly comprises the following components in sequence from the head to the tail: 32/32, 48/24, 48/48, 48/48, 48/48, 64/46, 64/64, 64/64, ZME12/24, ZME12/24, 48/48, 48/48, ZME12/24, 48/48, K45 °/5/48, K45 °/5/48, 64/64, 64/64, 64/64, 48/48, 64/64, 64/64, 32/16L, K45 °/5/48, K45 °/5/48, K45 °/5/48, K45 °/5/48, 48/48, K45 °/5/48, K45 °/5/48, K30 °/7/64, 48/48, 48/48, 48/48, 48/48, 64/64, 64/64, 48/48A; the length of the screw combination is 1888 mm.
Example 2
A preparation method of polyester resin with multiple oxygen-containing functional groups comprises the following steps:
(R1) pretreatment before reaction: placing polyester resin at a lower air inlet of a PECVD reaction cavity, vacuumizing the PECVD reaction cavity, continuously introducing oxygen, and controlling the air pressure of the PECVD reaction cavity to be 4 Pa;
(R2), plasma enhanced chemical vapor deposition: exciting oxygen into plasma under the action of an excitation source and reacting with polyester resin to obtain the oxygen-containing functional polyester resin.
The polyester resin is polyethylene terephthalate; the intrinsic viscosity of the polyethylene terephthalate was 0.7 dL/g.
In the step (R2), the excitation source is a microwave, the output power of the excitation source is 200W, and the reflection power of the excitation source is 1W; the reaction time was 1 h.
The polyester resin is polyester powder with the particle size of 6.5 mu m.
The step (R2) further comprises: after the plasma reacts with the polyester resin, the PECVD reaction cavity stops the action of the excitation source and the introduction of oxygen, and the PECVD reaction cavity is cooled to normal temperature under the condition of the environmental pressure of 4 Pa.
The polyester resin containing multiple oxygen functional groups is prepared by the preparation method of the polyester resin containing multiple oxygen functional groups.
The application of the multifunctional oxygen-containing polyester resin is that the multifunctional oxygen-containing polyester resin is applied to a polyester composite material.
The polyester composite material comprises the following raw materials in parts by weight:
the antioxidant is formed by mixing a hindered phenol main antioxidant and a thioether auxiliary antioxidant in a weight ratio of 1: 2; the hindered phenol main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) according to the weight ratio of 5: 1, mixing; the thioether auxiliary antioxidant is dilauryl thiodipropionate and 2, 4-di (n-octyl thiomethylene) -6-methylphenol according to the weight ratio of 1: 1 are mixed.
The flame retardant is brominated polycarbonate; the flame-retardant synergist is an organic silicon flame retardant with the relative molecular weight of 20000. The organic silicon flame retardant is polydiethylsiloxane.
The glass fiber is flat glass fiber, and the chopped length of the glass fiber is 4.5 mm.
The preparation method of the polyester composite material comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), premixing the polyester resin with the multi-oxygen-containing functional group and the diffusion oil in a high-speed mixer for 1min, then blending the premixed polyester resin with other raw materials for 1min, discharging, and carrying out extrusion granulation by a double-screw extruder under the condition of screw combination with certain strength shearing to obtain the polyester composite material.
The processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 170 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ of head temperature and 320r/min of screw rotation speed.
The screw rod combination comprises the following elements from the machine head to the machine tail in sequence: 32/32, 48/24, 48/48, 48/48, 48/48, 64/46, 64/64, 64/64, ZME12/24, ZME12/24, 48/48, 48/48, ZME12/24, 48/48, K45 °/5/48, K45 °/5/48, 64/64, 64/64, 64/64, 48/48, 64/64, 64/64, 32/16L, K45 °/5/48, K45 °/5/48, K45 °/5/48, K45 °/5/48, 48/48, K45 °/5/48, K45 °/5/48, K30 °/7/64, 48/48, 48/48, 48/48, 48/48, 64/64, 64/64, 48/48A; the length of the screw combination is 1888 mm.
Example 3
A preparation method of polyester resin with multiple oxygen-containing functional groups comprises the following steps:
(R1) pretreatment before reaction: placing polyester resin at a lower air inlet of a PECVD reaction cavity, vacuumizing the PECVD reaction cavity, continuously introducing oxygen, and controlling the air pressure of the PECVD reaction cavity to be 10 Pa;
(R2), plasma enhanced chemical vapor deposition: exciting oxygen into plasma under the action of an excitation source and reacting with polyester resin to obtain the oxygen-containing functional polyester resin.
The polyester resin is polybutylene terephthalate and poly terephthalic acid 1, 4-cyclohexane dimethanol ester according to the weight ratio of 3: 1, mixing; the intrinsic viscosity of the polybutylene terephthalate is 0.7 dL/g; the intrinsic viscosity of the poly (1, 4-cyclohexanedimethanol terephthalate) is 0.7 dL/g.
In the step (R2), the excitation source is radio frequency, the output power of the excitation source is 300W, and the reflection power of the excitation source is 30W; the reaction time was 2 h.
The polyester resin is polyester powder with the particle size of 10 mu m.
The step (R2) further comprises: after the plasma reacts with the polyester resin, the PECVD reaction cavity stops the action of the excitation source and the introduction of oxygen, and the PECVD reaction cavity is cooled to normal temperature under the condition of the atmospheric pressure of 10 Pa.
The polyester resin containing multiple oxygen functional groups is prepared by the preparation method of the polyester resin containing multiple oxygen functional groups.
The application of the multifunctional oxygen-containing polyester resin is that the multifunctional oxygen-containing polyester resin is applied to a polyester composite material.
The polyester composite material comprises the following raw materials in parts by weight:
the antioxidant is a hindered phenol main antioxidant and a thioether auxiliary antioxidant in a weight ratio of 1: 5, mixing the components; the hindered phenol main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) according to the weight ratio of 5: 3, mixing; the thioether auxiliary antioxidant is dilauryl thiodipropionate and 2, 4-di (n-octyl thiomethylene) -6-methylphenol according to the weight ratio of 3: 1 are mixed.
The flame retardant is brominated polycarbonate; the flame-retardant synergist is a silicone flame retardant with the relative molecular weight of 38000. The organic silicon flame retardant is polymethylsiloxane.
The glass fiber is high-modulus glass fiber, and the chopped length of the glass fiber is 2.0 mm. The elastic modulus of the high-modulus glass fiber is 95.0 GPa.
The preparation method of the polyester composite material comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), premixing the polyester resin with the multi-oxygen-containing functional group and the diffusion oil in a high-speed mixer for 3min, then blending the premixed polyester resin with other raw materials for 3min, discharging, and carrying out extrusion granulation by a double-screw extruder under the condition of screw combination with certain strength shearing to obtain the polyester composite material.
The processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 190 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, a head temperature of 250 deg.C, and a screw rotation speed of 400 r/min.
The screw rod combination comprises the following elements from the machine head to the machine tail in sequence: 32/32, 48/24, 48/48, 48/48, 48/48, 64/46, 64/64, 64/64, ZME12/24, ZME12/24, 48/48, 48/48, ZME12/24, 48/48, K45 °/5/48, K45 °/5/48, 64/64, 64/64, 64/64, 48/48, 64/64, 64/64, 32/16L, K45 °/5/48, K45 °/5/48, K45 °/5/48, K45 °/5/48, 48/48, K45 °/5/48, K45 °/5/48, K30 °/7/64, 48/48, 48/48, 48/48, 48/48, 64/64, 64/64, 48/48A; the length of the screw combination is 1888 mm.
Example 4
A preparation method of polyester resin with multiple oxygen-containing functional groups comprises the following steps:
(R1) pretreatment before reaction: placing polyester resin at a lower air inlet of a PECVD reaction cavity, vacuumizing the PECVD reaction cavity, continuously introducing oxygen, and controlling the air pressure of the PECVD reaction cavity to be 8 Pa;
(R2), plasma enhanced chemical vapor deposition: exciting oxygen into plasma under the action of an excitation source and reacting with polyester resin to obtain the oxygen-containing functional polyester resin.
The polyester resin is polyethylene terephthalate; the intrinsic viscosity of the polyethylene terephthalate is 0.8 dL/g.
In the step (R2), the excitation source is radio frequency, the output power of the excitation source is 230W, and the reflection power of the excitation source is 18W; the reaction time was 1.2 h.
The polyester resin is polyester powder with the particle size of 7 mu m.
The step (R2) further comprises: after the plasma reacts with the polyester resin, the PECVD reaction cavity stops the action of the excitation source and the introduction of oxygen, and the PECVD reaction cavity is cooled to normal temperature under the condition of the ambient pressure of 8 Pa.
The polyester resin containing multiple oxygen functional groups is prepared by the preparation method of the polyester resin containing multiple oxygen functional groups.
The application of the multifunctional oxygen-containing polyester resin is that the multifunctional oxygen-containing polyester resin is applied to a polyester composite material.
The polyester composite material comprises the following raw materials in parts by weight:
the antioxidant is formed by mixing a hindered phenol main antioxidant and a thioether auxiliary antioxidant according to the weight ratio of 1: 4; the hindered phenol main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) according to the weight ratio of 5: 1.2 mixing; the thioether auxiliary antioxidant is dilauryl thiodipropionate and 2, 4-di (n-octyl thiomethylene) -6-methylphenol according to the weight ratio of 2.4: 1 are mixed.
The flame retardant is brominated polystyrene and brominated epoxy according to the weight ratio of 1: 1, mixing; the flame-retardant synergist is an organic silicon flame retardant with the relative molecular weight of 25000. The organic silicon flame retardant is polymethylsiloxane.
The glass fiber is flat glass fiber, and the chopped length of the glass fiber is 2.5 mm.
The preparation method of the polyester composite material comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), premixing the polyester resin with the multi-oxygen-containing functional group and the diffusion oil in a high-speed mixer for 1.2min, then blending the polyester resin with other raw materials for 1.2min, discharging, and extruding and granulating by a double-screw extruder under the condition of screw combination with certain strength shearing to obtain the polyester composite material.
The processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 175 ℃, 195 ℃, 198 ℃, 205 ℃, 215 ℃, 225 ℃, 220 ℃, 215 ℃, 225 ℃, 245 ℃ of the head temperature and 350r/min of the screw rotation speed.
The screw rod combination comprises the following elements from the machine head to the machine tail in sequence: 32/32, 48/24, 48/48, 48/48, 48/48, 64/46, 64/64, 64/64, ZME12/24, ZME12/24, 48/48, 48/48, ZME12/24, 48/48, K45 °/5/48, K45 °/5/48, 64/64, 64/64, 64/64, 48/48, 64/64, 64/64, 32/16L, K45 °/5/48, K45 °/5/48, K45 °/5/48, K45 °/5/48, 48/48, K45 °/5/48, K45 °/5/48, K30 °/7/64, 48/48, 48/48, 48/48, 48/48, 64/64, 64/64, 48/48A; the length of the screw combination is 1888 mm.
Comparative example 1
This comparative example differs from example 1 in that:
the polyester composite material uses polyester resin instead of poly-oxygen functional polyester resin; the polyester resin is polybutylene terephthalate; the intrinsic viscosity of the polybutylene terephthalate is 0.8 dL/g.
Comparative example 2
This comparative example differs from example 1 in that:
the polyester composite material uses polyester resin instead of poly-oxygen functional polyester resin; the polyester resin is polybutylene terephthalate; the intrinsic viscosity of the polybutylene terephthalate is 0.8 dL/g. The polyester composite material was further added with 5 parts by weight of a compatibilizer SAG-001 (Hipport molecular materials science and technology Co., Ltd., Nantong Ri.).
Comparative example 3
This comparative example differs from example 1 in that:
the chopped length of the glass fiber is 1.5 mm.
Comparative example 4
This comparative example differs from example 1 in that:
the chopped length of the glass fiber is 5 mm.
Comparative example 5
This comparative example differs from example 1 in that:
the screw rod combination comprises the following elements from the machine head to the machine tail in sequence: 32/32, 48/24, 64/46, 64/64, 64/64, 48/48, 48/48, 48/48, ZME12/24, ZME12/24, 48/48, 48/48, ZME12/24, 48/48, K45 °/5/48, K45 °/5/48, 64/64, 64/64, 64/64, 48/48, 64/64, 64/64, 32/16L, K45 °/5/48, K45 °/5/48, K45 °/5/48, K45 °/5/48, 48/48, K45 °/5/48, K45 °/5/48, K30 °/7/64, 48/48, 48/48, 48/48, 48/48, 64/64, 64/64, 48/48A; the length of the screw combination is 1888 mm.
Example 5
I. In the method of preparing the polyester composite according to examples 1 to 4 and comparative examples 1 to 5, in the preparation process, the bracing effect of the polyester composite after extrusion through a twin-screw extruder was observed; II. The polyester composite materials prepared in the examples 1 to 4 and the comparative examples 1 to 5 are respectively tested for glass fiber retention length, unnotched cantilever beam impact strength, notched cantilever beam impact strength, tensile strength, bending strength and bending modulus; the test results are shown in table 1 below:
TABLE 1
The method for testing the glass fiber retention length comprises the steps of putting the polyester composite material into a muffle furnace, burning out the polyester composite material at the temperature of 800 ℃, taking out the glass fiber, and observing and measuring the length of the glass fiber by using a coordinate microscope.
As can be seen from table 1 above, from example 1, comparative example 1 and comparative example 2, in the present application, example 1 can achieve better mechanical properties and reinforcing effect without adding a compatibilizer, which can show that the multi-oxygen-containing functional group polyester resin used in example 1 exerts the effect of the compatibilizer to improve the compatibility of the material. From the embodiment 1, the comparative example 3 and the comparative example 4, the chopped length of the glass fiber is 2.0-4.5mm, and the polyester composite material obtained by combining the specific screw combination of the double-screw extruder has better mechanical property and better bracing effect, so that the subsequent product processing is facilitated, and the rough surface of the injection molding workpiece or the exposure of glass fibers is avoided. Compared with a comparative example 5, the specific screw combination shearing force adopted in the embodiment 1 is particularly suitable for the polyester composite material prepared in the application, the shearing force is moderate, the phenomenon that glass fiber is sheared to cause breakage of the drawn material is avoided, the improvement of the fiber content and the mechanical property is facilitated, the polyester composite material has higher impact strength, and meanwhile, the warping degree of the polyester composite material can be reduced.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (4)
1. A polyester composite material using a multifunctional oxygen-containing polyester resin is characterized in that: the feed comprises the following raw materials in parts by weight:
40-60 parts of multi-oxygen functional polyester resin
10-20 parts of flame retardant
3-5 parts of flame-retardant synergist
10-30 parts of glass fiber
0.1 to 0.2 portion of antioxidant
0.1 to 0.2 portion of diffusion oil
0.5-1.0 part of other auxiliary agents;
the preparation method of the polyester composite material comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2) premixing the polyester resin with the multi-oxygen-containing functional group and the diffusion oil in a high-speed mixer for 1-3min, then blending the premixed polyester resin with other raw materials for 1-3min, discharging, and extruding and granulating by a double-screw extruder under the condition of screw combination with certain strength shearing to obtain the polyester composite material;
the screw rod combination comprises the following elements from the machine head to the machine tail in sequence: 32/32, 48/24, 48/48, 48/48, 48/48, 64/46, 64/64, 64/64, ZME12/24, ZME12/24, 48/48, 48/48, ZME12/24, 48/48, K45 °/5/48, K45 °/5/48, 64/64, 64/64, 64/64, 48/48, 64/64, 64/64, 32/16L, K45 °/5/48, K45 °/5/48, K45 °/5/48, K45 °/5/48, 48/48, K45 °/5/48, K45 °/5/48, K30 °/7/64, 48/48, 48/48, 48/48, 48/48, 64/64, 64/64, 48/48A; the length of the screw combination is 1888-2000 mm;
the glass fiber is high-modulus glass fiber or flat glass fiber, and the chopped length of the glass fiber is 2.0-4.5 mm;
the preparation method of the polyester resin with multiple oxygen-containing functional groups comprises the following steps:
(R1) pretreatment before reaction: placing polyester resin at a lower air inlet of a PECVD reaction cavity, vacuumizing the PECVD reaction cavity, continuously introducing oxygen, and controlling the air pressure of the PECVD reaction cavity to be 4-10 Pa;
(R2), plasma enhanced chemical vapor deposition: exciting oxygen into plasma under the action of an excitation source and reacting with polyester resin to obtain the oxygen-containing functional polyester resin.
2. The polyester composite material using the multifunctional oxygen-containing polyester resin as claimed in claim 1, wherein: in the step (R2), the excitation source is radio frequency, direct current high voltage, pulse or microwave, the output power of the excitation source is 200-300W, and the reflection power of the excitation source is 0-30W; the reaction time is 1-2 h.
3. The polyester composite material using the multifunctional oxygen-containing polyester resin as claimed in claim 1, wherein: the polyester resin is polyester powder with the particle size of 6.5-10 mu m.
4. The polyester composite material using the multifunctional oxygen-containing polyester resin as claimed in claim 1, wherein: the step (R2) further comprises: after the plasma reacts with the polyester resin, the PECVD reaction cavity stops the action of the excitation source and the introduction of oxygen, and the PECVD reaction cavity is cooled to normal temperature under the condition of the environmental pressure of 4-10 Pa.
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