CN110713700A - Polyester composite material and preparation method and application thereof - Google Patents

Abstract

The invention relates to a polyester composite material and a preparation method and application thereof. The polyester composite material is prepared by taking a polyester block copolymer with a silicon unit as a raw material; also includes inorganic fiber and additive. The polyester composite material has higher strength, excellent hydrolysis resistance, low temperature resistance and plugging resistance, is suitable for application in high-temperature and high-humidity environments, and provides a new and better choice for the selection of components such as automobile connectors, plugs and the like.

Description

Polyester composite material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of polymer composite materials, and particularly relates to a polyester composite material and a preparation method and application thereof.

Background

The polyester material is one of five engineering plastics, mainly refers to PBT, and is a semi-crystalline thermoplastic resin with a Chinese name of polybutylene terephthalate. The high-modulus high-elasticity high-strength high-elasticity high-heat-resistance high-strength high-tenacity. However, the composite materials used at present have shortcomings in low temperature resistance, hydrolysis resistance, insertion and extraction resistance and the like.

In the automotive field, a large number of wire harnesses are connected by connectors to achieve the functions of signal transmission and control devices, and the connectors are mainly made of composite materials of PBT and fibers. However, since automobiles basically work outdoors, and the automobiles run in various environments such as severe cold, severe summer heat, humidity, dryness and the like, the existing polyester composite materials are sensitive to gaps, and have poor toughness particularly at low temperature, so that the service time and the comfort experience of the automobiles are influenced. In the field of household appliances, the freezing chamber works in an environment of 20 ℃ below zero throughout the year, and injection-grade PBT is easy to become brittle and burst in an environment of 40 ℃ below zero, so that the application is limited. Although the mainstream toughening agent in the market can improve the toughness of the PBT at normal temperature, the low-temperature toughening effect on the PBT is not ideal. CN103450647A proposes that PBT is modified by using an amino acid grafted ethylene copolymer, so that the low-temperature impact strength of the material is improved; but the grafting rate of amino acid is limited, the toughness is not obviously improved, and the residual amino acid monomer influences the overall performance of the material. Therefore, if the toughness, especially the low-temperature toughness, of the material can be improved, the method has very important practical significance for widening the application field.

Meanwhile, polyester is a high molecular polymer obtained by condensation of diacid and diol and removal of water molecules, and ester bonds endow the polyester material with certain polarity. The higher the polarity, the more moisture-absorbing and adsorbing other small molecules or particulate impurities, and the lower the polarity, the less moisture-absorbing and adsorbing other small molecules or particulate impurities. Therefore, the stability of the polyester in a humid environment is improved, the functions and the service time of the product prepared by the polyester are improved, and the application field of the product can be widened.

In addition, most parts prepared from the polyester materials are required to be installed with other parts, and plugging and buckling are required, so that the installation is firm and stable, and the material buckle is broken due to repeated plugging and unplugging, so that the parts are damaged and fail. Therefore, the plugging resistance of the material is improved, and particularly the plugging resistance in a severe environment can be obviously improved.

Disclosure of Invention

The invention aims to overcome the defects in the prior art, and the novel polyester composite material is obtained by compounding the polyester block copolymer containing the silicon unit and the fiber, so that the hydrolysis resistance, the low temperature resistance and the plugging resistance of the conventional polyester composite material are improved, and the possibility is provided for the application expansion of the material.

The technical scheme adopted by the invention is as follows.

A polyester composite material is prepared from a polyester block copolymer with a silicon unit. By blending the polyester block copolymer with the silicon unit and the inorganic fiber, the polyester composite material is superior to the common polyester inorganic fiber reinforced material in the aspects of bending strain, notch impact strength, low-temperature notch impact strength, performance after damp-heat aging and the like.

Preferably, the polyester composite is made from A, B, C comprising, by weight,

(I) a is a polyester block copolymer containing silicon units, the content of the polyester block copolymer is 30 weight parts < A <100 weight parts, and the structural formula is shown as follows:

-M-N- (formula α)

In the formula alpha, M is one or more of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polycyclohexylenedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN) and the like;

the structural formula of N is shown as follows:

in the formula beta, R₃And R₄Is one of methyl, ethyl or phenyl; r₅Is composed of

Or

(II) B is an inorganic fiber, the content of which is 0 weight part < B <50.1 weight parts;

(III) C is an additive, and the content of the additive is more than or equal to 0 weight part and less than 10 weight parts.

Further, the intrinsic viscosity of the polyester block copolymer is 0.6 to 2.0dL/g, preferably 0.70 to 1.33dL/g, and more preferably 0.78 to 1.10 dL/g.

Further, in the polyester block copolymer, the content of M is 0 parts by weight < M.ltoreq.99 parts by weight, preferably 50 parts by weight < M.ltoreq.95 parts by weight, more preferably 80 parts by weight < M.ltoreq.95 parts by weight. The content of N is 0 weight part < N.ltoreq.60 weight parts, preferably 1 weight part < N.ltoreq.40 weight parts, more preferably 3 weight parts < N.ltoreq.20 weight parts.

When M is PET, PTT, PBT or PCT, R in N₅Has the structural formula

When M is PEN or PBN, R in N₅Has the structural formula

Further, the inorganic fiber is selected from one or more of glass fiber, basalt fiber, quartz fiber, ceramic fiber, boron fiber, silicon nitride fiber or carbon fiber, etc., preferably glass fiber, basalt fiber or quartz fiber, and most preferably glass fiber. Wherein the alkali content (sodium oxide content) of the glass fibers is not more than 13%, preferably not more than 8%, most preferably less than 2% (i.e. belonging to alkali-free glass fibers).

Further, the additive is selected from one or more of antioxidants, heat stabilizers, ultraviolet light stabilizers, coloring agents (including dyes and pigments), anti-hydrolysis agents, mold release agents, lubricants, plasticizers, dispersing aids, reinforcing fillers, flow modifiers, chain extenders and flame retardants.

Another object of the present invention is to provide a method for preparing the above polyester composite material, comprising:

(1) introducing polysilane molecules into a polyester molecular structure, and obtaining a polyester block copolymer A by a copolymerization method;

(2) and then carrying out inorganic fiber reinforcement modification on the polyester block copolymer to obtain the polyester composite material in a blending mode.

Wherein, the preparation of the polyester block copolymer A in the step (1) specifically comprises the following steps: esterification reaction, pre-polycondensation reaction and polycondensation reaction; further, if necessary, a solid-phase thickening reaction may be performed. The method comprises the following specific steps:

s1, carrying out esterification reaction on dibasic acid and dihydric alcohol to generate an intermediate product M;

s2, the dibasic acid which is the same as the dibasic acid S1 and the compound shown in the formula (III) are subjected to esterification reaction to generate an intermediate product N;

s3, mixing M and N for pre-polycondensation reaction;

s4, continuing to perform polycondensation reaction to generate a polyester block copolymer A containing silicon units;

in S1, the dibasic acid may be terephthalic acid or terephthalic acid; the diol may be ethylene glycol, propylene glycol, butylene glycol, or 1, 4-Cyclohexanedimethanol (CHDM); the molar ratio of the dibasic acid to the dihydric alcohol is 1:1-1: 1.5.

In S2, the compound of formula (III) has the following structure:

preferably, the compound represented by the formula (III) may be selected from α, ω -dihydroxyethyl polydimethylsiloxane, α, ω -dihydroxyethyl polydiethylsiloxane, α, ω -dihydroxyethyl polymethylphenylsiloxane, α, ω -dihydroxyethyl polydiphenylsiloxane, and the like.

The molar ratio of the dibasic acid to the compound shown in the formula (III) is 1:1.2-1: 1.5.

In the above-mentioned S1/S2, the catalysis is preferably carried out using a catalyst. The catalyst can be one or more selected from germanium oxide, manganese acetate, zinc acetate, tetrabutyl titanate, antimony trioxide, ethylene glycol antimony and ethylene glycol titanium. The mass of the catalyst is preferably 0.01-0.1% of the total mass of the reaction raw materials.

In the above S1, it is preferable to use a mixed system of a catalyst and a glycol, the mixed system being prepared by a method comprising: and (3) placing the dihydric alcohol and the catalyst into a reaction kettle according to the proportion, heating and boiling for 2-4 hours under a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 170-200 ℃, and cooling. Wherein the molar ratio of the dihydric alcohol to the catalyst is 1:3-1: 6.

In the above S1/S2, the esterification reaction may be carried out under conventional conditions. As a preferred embodiment: the conditions of the esterification reaction in step 1) are preferably: the temperature is 160-245 ℃, and the vacuum degree is 40-45 KPa; the esterification reaction conditions in the step 2) are as follows: the temperature is 160-245 ℃, and the vacuum degree is 40-45 KPa.

In the above S3, the pre-polycondensation reaction conditions are: the temperature is 180 ℃ and 310 ℃, the vacuum degree is 1.5-2.5KPa, and the reaction time is 30-60min generally;

in the above S4, the polycondensation reaction conditions are: the temperature is 180 ℃ and 310 ℃, the vacuum degree is 100Pa and 200Pa, and the reaction time is 60-240 min.

In the preparation process of the polyester block copolymer, the polycondensation process started in the esterification reaction is continuously carried out in a pre-polycondensation kettle, the pre-polycondensation reaction generates the polyester copolymer with low molecular weight, and the pre-polycondensation product enters a polycondensation reactor after passing through a pre-polycondensation discharge pump, a pre-polycondensation discharge filter and a pre-polycondensation discharge cooler. The polycondensation reaction produces a high molecular weight polyester block copolymer. The polycondensation product enters a granulator system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter and a polycondensation discharge distribution valve. Cooling and pelletizing to obtain the high molecular weight polyester block copolymer product.

However, the intrinsic viscosity of the polyester block copolymer obtained by the above method is relatively low. In order to increase the viscosity of the polyester block copolymer, the method of the present invention may further comprise subjecting the obtained polycondensation product to solid-phase tackifying reaction. The solid phase tackifying reaction can be carried out in a vacuum state (3-100Pa) or in an inert gas-shielded state (the flow rate of the inert gas is 0.5-5L/[ min KG tackifying particles ]). Preferably, the temperature of the solid phase tackifying reaction is 100-260 ℃, and the general reaction time is 4-36 hours. The specific reaction conditions can be determined according to actual needs.

As a preferred embodiment of the method for producing the obtained polyester block copolymer of the present invention, the method specifically comprises the steps of:

k1: preparation of slurry

Placing dicarboxylic acid and dihydric alcohol in a container (a preparation tank), and uniformly stirring to obtain a mixed material 1; wherein the molar ratio of the dicarboxylic acid to the diol is 1:1-1: 1.5;

placing the dibasic acid and the compound shown in the formula (III) into a container (a preparation tank), and uniformly stirring to obtain a mixed material 2; wherein the molar ratio of the dibasic acid to the compound shown in the formula (III) is 1:1.2-1: 1.5;

k2: catalyst formulation

Adding the dihydric alcohol and the catalyst into a container (a preparation tank) according to the molar ratio of 1:3-1:6, heating and boiling for 2-4 hours under a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 170-200 ℃, and cooling to obtain a catalyst mixed system;

k3: esterification reaction

Placing the mixed material 1 in a reaction kettle (esterification kettle), adding a catalyst mixed system for esterification reaction until no water is generated, and generating oligomer OM 1; wherein the mass ratio of the added catalyst to the mixed material 1 is 0.01-0.1%; the esterification reaction conditions are as follows: the temperature is 160-245 ℃, the vacuum degree is 40-45KPa, and the reaction time is 1-3 hours;

placing the mixed material 2 in a reaction kettle (esterification kettle), adding a catalyst mixed system for esterification reaction until no water is generated; generating oligomer OM2, namely the compound shown in the formula (beta);

wherein the mass ratio of the added catalyst to the mixed material 2 is 0.01-0.1%; the esterification reaction conditions are as follows: the temperature is 160-245 ℃, the vacuum degree is 40-45KPa, and the reaction time is 1-3 hours;

k4: prepolycondensation reaction

Placing the oligomer OM1 and the oligomer OM2 in a reaction kettle (pre-polycondensation kettle) to perform pre-polycondensation reaction to generate a pre-polycondensation product (namely a low-molecular-weight polyester copolymer); wherein the proportion of the mass of the oligomer OM1 to the sum of the masses of the oligomer OM1 and the oligomer OM2 is 0.1-50%; the pre-polycondensation reaction conditions are as follows: the temperature is 180 ℃ and 310 ℃, the vacuum degree is 1.5-2.5KPa, and the reaction time is 30-60 min.

K5: polycondensation reaction

Putting the pre-polycondensation product obtained in the step K4 into a reaction kettle (a polycondensation reactor) for polycondensation reaction to generate a compound shown in the formula (I) (namely, a polyester block copolymer with high molecular weight); the polycondensation reaction conditions are as follows: the temperature is 180-; the intrinsic viscosity of the obtained polyester block copolymer is 0.5-1.0 dL/g;

k6: solid phase tackifying reaction

Feeding the polyester block copolymer particles obtained by the polycondensation reaction into a tackifying kettle, carrying out solid phase reaction at a set temperature of 100 ℃ and 260 ℃ under the vacuum state of 3-100Pa or the inert gas protection state with the flow rate of inert gas of 0.5-5L/[ min. KG tackifying particles, and the reaction time of 4-36 hours to obtain the polyester block copolymer.

The resulting polyester block copolymer has an intrinsic viscosity of 0.6 to 2.0dL/g, such as 0.8 to 2.0dL/g, 0.70 to 1.33dL/g, 0.78 to 1.10 dL/g.

The invention further optimizes the reaction conditions according to the characteristics of the raw materials. Specifically, the method comprises the following steps:

when the dicarboxylic acid is 2, 6-naphthalenedicarboxylic acid in the step K1, the pre-polycondensation reaction temperature is 250-310 ℃, the polycondensation reaction temperature is 250-310 ℃, and the solid phase tackifying reaction temperature is preferably 200-240 ℃.

When the dicarboxylic acid is terephthalic acid and the diol is 1, 4-Cyclohexanedimethanol (CHDM) in the step K1, the pre-polymerization reaction temperature ranges from 280 ℃ to 310 ℃, the polycondensation reaction temperature ranges from 280 ℃ to 310 ℃, and the solid phase tackifying reaction temperature is preferably 240 ℃ to 260 ℃.

When the dicarboxylic acid is terephthalic acid, the diol is one diol other than 1, 4-Cyclohexanedimethanol (CHDM) or a mixture of two or more diols in the step K1, the pre-polycondensation reaction temperature ranges from 200 ℃ to 250 ℃, the polycondensation reaction temperature ranges from 200 ℃ to 250 ℃, and the solid phase tackifying reaction temperature is preferably 180 ℃ to 220 ℃.

All the raw materials adopted in the steps of the invention can be commercially obtained.

Wherein, the step (2) specifically comprises the following steps:

s5 drying: drying the obtained polyester block copolymer and inorganic fiber at 80-120 deg.C for 2-4 hr, and drying the rest additives at corresponding temperature.

S6, batching: the polyester block copolymer (A), the inorganic fiber (B) and the additive (C) are weighed according to a set proportion, and the requirement that A + B + C is 100 is met.

S7 extrusion: adding the materials into a double-screw extruder, carrying out melt extrusion, bracing, cooling and granulating.

In order to ensure that the prepared composite material has good material performance, the extrusion equipment preferably adopts a double-screw extruder, the length-diameter ratio of the extruder is 32-48:1, and/or the extrusion temperature is 170-300 ℃, and/or the screw rotation speed during extrusion is 180-900 rpm.

The polyester block copolymer (formula. alpha.) described in step S6 may be PET containing silicon units, may be PTT containing silicon units, may be PBT containing silicon units, may be PCT containing silicon units, may be PEN containing silicon units, may be PBN containing silicon units, preferably PBT containing silicon units.

The inorganic fibers described in step S6 may be glass fibers, basalt fibers, quartz fibers, ceramic fibers, boron fibers, silicon nitride fibers, carbon fibers, or the like, and the glass fibers, the basalt fibers, and the quartz fibers are preferably selected, and the glass fibers are most preferably selected. The alkali content (sodium oxide content) in the glass fiber is not more than 13%, the alkali content of the glass fiber is preferably not more than 8%, and the alkali content of the glass fiber is preferably less than 2% (alkali-free glass fiber).

The additives of step S6 are selected from the group consisting of antioxidants, heat stabilizers, ultraviolet light stabilizers, colorants including dyes and pigments, anti-hydrolysis agents, mold release agents, lubricants, plasticizers, dispersion aids, reinforcing fillers, flow modifiers, chain extenders, flame retardants, and any combination thereof.

The invention also provides the application of the polyester composite material in the fields of electronic appliances, automobiles, illumination, machinery, spinning, communication, films or instruments and meters.

Compared with the prior art, the invention has the following advantages:

firstly, the polyester composite material containing the silicon unit is excellent in mechanical property and low-temperature resistance, and has low surface tension, so that the application range of the existing polyester material is greatly expanded.

Secondly, the anti-plugging performance of the polyester composite material containing the silicon unit is obviously improved, so that the service cycle of a product prepared by the polyester composite material is greatly prolonged, and the durability of a downstream product is enhanced.

Thirdly, the polyester segmented copolymer is prepared by adopting a direct polymerization method, wherein silicon molecules are uniformly distributed in a molecular chain of the polyester resin, so that the phenomenon of layering or incompatibility caused by the compatibility problem in the conventional blending mode (silicone rubber or silicone resin and polyester resin are blended by a double-screw extruder) is avoided; meanwhile, the problem that the residual micromolecules are in the final blend and the volatile matters are high due to the fact that small-molecule organic silicon molecules containing reaction groups are blended with polyester resin through a double-screw extruder and the reaction is insufficient due to short residence time in the double screws is solved.

Fourthly, the preparation method adopted by the invention is to esterify the silicon-containing monomer and the non-silicon-containing monomer respectively and then polymerize the monomers, so that the reaction is easier to control according to the requirements, and the polyester block copolymer with certain regularity is convenient to obtain; meanwhile, the silicon-containing monomer is esterified first, so that the reaction is easier to control.

Fifth, the preparation method provided by the invention finally adopts a solid-phase polymerization mode with mild reaction conditions to synthesize the high molecular weight polyester block copolymer which can not be prepared by direct polycondensation, thereby not only achieving the expected effect, but also avoiding the defects of large energy consumption, harsh reaction conditions, high requirements on equipment and difficulty in controlling the process conditions of the product in the conventional polycondensation mode. The preparation method of the polyester block copolymer provided by the invention is optimized on the basis of the existing polyester production method, is simple and convenient, and is easy to control and realize industrial production.

And sixthly, the preparation method provided by the invention uses a double-screw extruder to prepare the composite material of the polyester block copolymer and the inorganic fiber, and has simple and universal equipment and easy popularization.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.

The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.

The following methods were used for the relevant tests of the invention:

the intrinsic viscosity: measured according to ASTM D445.

Bending strength and bending strain: measured according to ASTM D790.

Impact strength: measured according to ASTM D256.

And (3) low temperature resistance test: the specimens were placed in a cold box (-40 ℃) for 24h and the material was tested for low temperature notched impact strength.

Surface tension: and (5) testing by using a dyne pen, and recording the dyne value.

Hydrolysis resistance and aging test: aging was carried out at 85 ℃ and 85% humidity for 1000 hours, after which the relevant items were tested as required.

And (3) testing the insertion and extraction force resistance: and (3) according to the specification of an EIA-364-13C standard, injection-molding the prepared material into a USB plastic part sample, testing the extraction force and the insertion force of the sample, wherein the insertion force is not more than 3.5KG and the extraction force is not less than 1.0KG, repeatedly testing for many times, and recording the starting times which do not meet the requirements.

Example 1 preparation of polyester composite

Preparation of (mono) polyester block copolymer

1.1 slurry preparation:

1) dicarboxylic acid (PTA) and diol (BDO, namely 1,4 butanediol) enter a slurry preparation tank U1 through a metering system respectively and are uniformly stirred to obtain slurry S1, wherein the PTA is 773G (G means gram, the same below), and the BDO is 520G.

2) The dicarboxylic acid PTA and R2 (alpha, omega-hydroxypropyl polydimethylsiloxane) used in the slurry 1) enter a slurry preparation tank U2 through a metering system respectively, and are uniformly stirred to be recorded as slurry S2, wherein the PTA is 154G, and the R2 is 80G.

1.2 catalyst preparation: adding 100G of dihydric alcohol (BDO) and 158.9G of catalyst C (tetrabutyl titanate) into a preparation tank U3, heating and boiling for 2-3 hours in a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 180 ℃, and transferring the prepared catalyst into a catalyst feeding tank after cooling.

1.3 esterification: and (3) pumping the slurry S1 in the slurry tank U1 into an esterification kettle E1 through a slurry pump, delivering the prepared catalyst C into the esterification kettle E1 through a gear pump, and carrying out esterification reaction under the action of the catalyst until no water is generated, so as to obtain the oligomer OM 1. The amount of the catalyst added was 0.05% based on the mass ratio C/S1 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate reaches 99.2 percent.

1.4 esterification: and (3) delivering the slurry S2 in the slurry tank U2 into an esterification kettle E2 through a slurry pump, delivering the prepared catalyst into the esterification kettle E2 through a gear pump, carrying out esterification reaction under the action of the catalyst until no water is generated, and generating an oligomer OM 2. The amount of the catalyst added was 0.05% based on the mass ratio C/S2 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate is 99 percent.

1.5 pre-polycondensation reaction: the oligomers in esterification kettles E1 and E2 are respectively fed into the pre-polycondensation kettle in proportion, wherein the proportion OM2/(OM1+ OM2) added by OM2 in esterification kettle E2 is 5%. The initial polycondensation process in the esterification reaction is continuously carried out in a pre-polycondensation kettle, the pre-polycondensation reaction temperature is 245 ℃, the vacuum degree is-2 KPa, the reaction time is 40min, a low molecular weight polyester copolymer is generated, and the pre-polycondensation product enters a polycondensation reactor through a pre-polycondensation discharge pump, a pre-polycondensation discharge filter and a pre-polycondensation discharge cooler.

1.6 polycondensation reaction: and (3) feeding the pre-polycondensation product into a polycondensation reactor from the pre-polycondensation unit, and continuously reacting the prepolymer, wherein the polycondensation reaction temperature is 248 ℃, the vacuum degree is 120Pa, and the reaction time is 200min, so that the high-molecular-weight polyester block copolymer is generated. The polycondensation product enters a granulator system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter and a polycondensation discharge distribution valve. Cooling and pelletizing to obtain the high molecular weight polyester block copolymer product.

1.7 solid-phase tackifying reaction: the polyester block copolymer particles obtained by the polycondensation reaction are sent into a tackifying kettle, and solid phase reaction is carried out at a set temperature under the vacuum state of 10Pa or the protection of inert gas, and the reaction time is 20 hours.

The intrinsic viscosity of the resulting polyester block copolymer was 0.92 dL/g. The temperature was set at 200 ℃.

Blending modification of (di) polyester block copolymer and glass fiber

69.8 parts by weight of the obtained polyester block copolymer is weighed and dried at 80-120 ℃ for 2-4 hours, and the moisture content is controlled to be less than 0.05 percent. The dried polyester block copolymer is fed into a twin-screw extruder from a metering feeder, and 0.1 part of antioxidant 168 and 1010 part of antioxidant are added respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; at the same time, 30 parts of alkali-free glass fiber (commercial number T436H) is added into a side feeding system, and the glass fiber composite material is prepared by extrusion, cooling, grain cutting, uniform mixing and packaging. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Example 2

Preparation of (mono) polyester block copolymer

1.1 slurry preparation:

1) dicarboxylic acid (PTA) and diol (BDO, namely 1,4 butanediol) enter a slurry preparation tank U1 through a metering system respectively and are uniformly stirred to obtain slurry S1, wherein the PTA is 773G (G means gram, the same below), and the BDO is 520G.

2) The dicarboxylic acid PTA and R2 (alpha, omega-hydroxypropyl polydimethylsiloxane) used in the slurry 1) enter a slurry preparation tank U2 through a metering system respectively, and are uniformly stirred to be recorded as slurry S2, wherein the PTA is 154G, and the R2 is 80G.

1.2 catalyst preparation: adding 100G of dihydric alcohol (BDO) and 158.9G of catalyst C (tetrabutyl titanate) into a preparation tank U3, heating and boiling for 2-3 hours in a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 180 ℃, and transferring the prepared catalyst into a catalyst feeding tank after cooling.

1.3 esterification: and (3) pumping the slurry S1 in the slurry tank U1 into an esterification kettle E1 through a slurry pump, delivering the prepared catalyst C into the esterification kettle E1 through a gear pump, and carrying out esterification reaction under the action of the catalyst until no water is generated, so as to obtain the oligomer OM 1. The amount of the catalyst added was 0.05% based on the mass ratio C/S1 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 24 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate reaches 99.2 percent.

1.4 esterification: and (3) delivering the slurry S2 in the slurry tank U2 into an esterification kettle E2 through a slurry pump, delivering the prepared catalyst into the esterification kettle E2 through a gear pump, carrying out esterification reaction under the action of the catalyst until no water is generated, and generating an oligomer OM 2. The amount of the catalyst added was 0.05% based on the mass ratio C/S2 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate is 99 percent.

1.5 pre-polycondensation reaction: the oligomers in the esterification kettles E1 and E2 are respectively fed into the pre-polycondensation kettle in proportion, wherein the proportion OM2/(OM1+ OM2) added by OM2 in the esterification kettle E2 is 10%. The initial polycondensation process in the esterification reaction is continuously carried out in a pre-polycondensation kettle, the pre-polycondensation reaction temperature is 245 ℃, the vacuum degree is-2 KPa, the reaction time is 40min, a low molecular weight polyester copolymer is generated, and the pre-polycondensation product enters a polycondensation reactor through a pre-polycondensation discharge pump, a pre-polycondensation discharge filter and a pre-polycondensation discharge cooler.

1.6 polycondensation reaction: and (3) feeding the pre-polycondensation product into a polycondensation reactor from the pre-polycondensation unit, and continuously reacting the prepolymer, wherein the polycondensation reaction temperature is 248 ℃, the vacuum degree is 120Pa, and the reaction time is 200min, so that the high-molecular-weight polyester block copolymer is generated. The polycondensation product enters a granulator system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter and a polycondensation discharge distribution valve. Cooling and pelletizing to obtain the high molecular weight polyester block copolymer product.

1.7 solid-phase tackifying reaction: the polyester block copolymer particles obtained by the polycondensation reaction are sent into a tackifying kettle, and solid phase reaction is carried out at a set temperature under the vacuum state of 10Pa or the protection of inert gas, and the reaction time is 20 hours.

The intrinsic viscosity of the resulting polyester block copolymer was 0.91 dL/g. The temperature was set at 200 ℃.

Blending modification of (di) polyester block copolymer and glass fiber

69.8 parts by weight of polyester block copolymer is weighed and dried for 2 to 4 hours at the temperature of between 80 and 120 ℃, and the moisture content is controlled to be less than 0.05 percent. The dried polyester block copolymer is fed into a twin-screw extruder from a metering feeder, and 0.1 part of antioxidant 168 and 1010 part of antioxidant are added respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; at the same time, 30 parts of alkali-free glass fiber (commercial number T436H) is added into a side feeding system, and the glass fiber composite material is prepared by extrusion, cooling, grain cutting, uniform mixing and packaging. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Example 3

Preparation of (mono) polyester block copolymer

1.1 slurry preparation:

1) dicarboxylic acid (PTA) and diol (BDO, namely 1,4 butanediol) enter a slurry preparation tank U1 through a metering system respectively and are uniformly stirred to obtain slurry S1, wherein the PTA is 773G (G means gram, the same below), and the BDO is 520G.

2) The dicarboxylic acid PTA and R2 (alpha, omega-hydroxypropyl polydimethylsiloxane) used in the slurry 1) enter a slurry preparation tank U2 through a metering system respectively, and are uniformly stirred to be recorded as slurry S2, wherein the PTA is 154G, and the R2 is 80G.

1.2 catalyst preparation: adding 100G of dihydric alcohol (BDO) and 158.9G of catalyst C (tetrabutyl titanate) into a preparation tank U3, heating and boiling for 2-3 hours in a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 180 ℃, and transferring the prepared catalyst into a catalyst feeding tank after cooling.

1.3 esterification: and (3) pumping the slurry S1 in the slurry tank U1 into an esterification kettle E1 through a slurry pump, delivering the prepared catalyst C into the esterification kettle E1 through a gear pump, and carrying out esterification reaction under the action of the catalyst until no water is generated, so as to obtain the oligomer OM 1. The amount of the catalyst added was 0.05% based on the mass ratio C/S1 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate reaches 99.2 percent.

1.4 esterification: and (3) delivering the slurry S2 in the slurry tank U2 into an esterification kettle E2 through a slurry pump, delivering the prepared catalyst into the esterification kettle E2 through a gear pump, carrying out esterification reaction under the action of the catalyst until no water is generated, and generating an oligomer OM 2. The amount of the catalyst added was 0.05% based on the mass ratio C/S2 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate is 99 percent.

1.5 pre-polycondensation reaction: the oligomers in esterification kettles E1 and E2 are respectively fed into the pre-polycondensation kettle in proportion, wherein the proportion OM2/(OM1+ OM2) added by OM2 in esterification kettle E2 is 15%. The initial polycondensation process in the esterification reaction is continuously carried out in a pre-polycondensation kettle, the pre-polycondensation reaction temperature is 245 ℃, the vacuum degree is-2 KPa, the reaction time is 40min, a low molecular weight polyester copolymer is generated, and the pre-polycondensation product enters a polycondensation reactor through a pre-polycondensation discharge pump, a pre-polycondensation discharge filter and a pre-polycondensation discharge cooler.

1.6 polycondensation reaction: and (3) feeding the pre-polycondensation product into a polycondensation reactor from the pre-polycondensation unit, and continuously reacting the prepolymer, wherein the polycondensation reaction temperature is 248 ℃, the vacuum degree is 120Pa, and the reaction time is 200min, so that the high-molecular-weight polyester block copolymer is generated. The polycondensation product enters a granulator system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter and a polycondensation discharge distribution valve. Cooling and pelletizing to obtain the high molecular weight polyester block copolymer product.

1.7 solid-phase tackifying reaction: the polyester block copolymer particles obtained by the polycondensation reaction are sent into a tackifying kettle, and solid phase reaction is carried out at a set temperature under the vacuum state of 10Pa or the protection of inert gas, and the reaction time is 20 hours.

The intrinsic viscosity of the resulting polyester block copolymer was 0.90 dL/g. The temperature was set at 200 ℃.

Blending modification of (di) polyester block copolymer and glass fiber

69.8 parts by weight of polyester block copolymer is weighed and dried for 2 to 4 hours at the temperature of between 80 and 120 ℃, and the moisture content is controlled to be less than 0.05 percent. The dried polyester block copolymer is fed into a twin-screw extruder from a metering feeder, and 0.1 part of antioxidant 168 and 1010 part of antioxidant are added respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; at the same time, 30 parts of alkali-free glass fiber (commercial number T436H) is added into a side feeding system, and the glass fiber composite material is prepared by extrusion, cooling, grain cutting, uniform mixing and packaging. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Example 4

Preparation of (mono) polyester block copolymer

1.1 slurry preparation:

1) dicarboxylic acid (PTA) and diol (BDO, namely 1,4 butanediol) enter a slurry preparation tank U1 through a metering system respectively and are uniformly stirred to obtain slurry S1, wherein the PTA is 773G (G means gram, the same below), and the BDO is 520G.

2) The dicarboxylic acid PTA and R2 (alpha, omega-hydroxypropyl polydimethylsiloxane) used in the slurry 1) enter a slurry preparation tank U2 through a metering system respectively, and are uniformly stirred to be recorded as slurry S2, wherein the PTA is 154G, and the R2 is 80G.

1.2 catalyst preparation: adding 100G of dihydric alcohol (BDO) and 158.9G of catalyst C (tetrabutyl titanate) into a preparation tank U3, heating and boiling for 2-3 hours in a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 180 ℃, and transferring the prepared catalyst into a catalyst feeding tank after cooling.

1.3 esterification: and (3) pumping the slurry S1 in the slurry tank U1 into an esterification kettle E1 through a slurry pump, delivering the prepared catalyst C into the esterification kettle E1 through a gear pump, and carrying out esterification reaction under the action of the catalyst until no water is generated, so as to obtain the oligomer OM 1. The amount of the catalyst added was 0.05% based on the mass ratio C/S1 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate reaches 99.2 percent.

1.4 esterification: and (3) delivering the slurry S2 in the slurry tank U2 into an esterification kettle E2 through a slurry pump, delivering the prepared catalyst into the esterification kettle E2 through a gear pump, carrying out esterification reaction under the action of the catalyst until no water is generated, and generating an oligomer OM 2. The amount of the catalyst added was 0.05% based on the mass ratio C/S2 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate is 99 percent.

1.5 pre-polycondensation reaction: the oligomers in the esterification kettles E1 and E2 are respectively fed into the pre-polycondensation kettle in proportion, wherein the proportion OM2/(OM1+ OM2) of OM2 in the esterification kettle E2 is 20%. The initial polycondensation process in the esterification reaction is continuously carried out in a pre-polycondensation kettle, the pre-polycondensation reaction temperature is 245 ℃, the vacuum degree is-2 KPa, the reaction time is 40min, a low molecular weight polyester copolymer is generated, and the pre-polycondensation product enters a polycondensation reactor through a pre-polycondensation discharge pump, a pre-polycondensation discharge filter and a pre-polycondensation discharge cooler.

1.6 polycondensation reaction: and (3) feeding the pre-polycondensation product into a polycondensation reactor from the pre-polycondensation unit, and continuously reacting the prepolymer, wherein the polycondensation reaction temperature is 248 ℃, the vacuum degree is 120Pa, and the reaction time is 200min, so that the high-molecular-weight polyester block copolymer is generated. The polycondensation product enters a granulator system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter and a polycondensation discharge distribution valve. Cooling and pelletizing to obtain the high molecular weight polyester block copolymer product.

1.7 solid-phase tackifying reaction: the polyester block copolymer particles obtained by the polycondensation reaction are sent into a tackifying kettle, and solid phase reaction is carried out at a set temperature under the vacuum state of 10Pa or the protection of inert gas, and the reaction time is 20 hours.

The intrinsic viscosity of the resulting polyester block copolymer was 0.93 dL/g. The temperature was set at 200 ℃.

Blending modification of (di) polyester block copolymer and glass fiber

69.8 parts by weight of polyester block copolymer is weighed and dried for 2 to 4 hours at the temperature of between 80 and 120 ℃, and the moisture content is controlled to be less than 0.05 percent. The dried polyester block copolymer is fed into a twin-screw extruder from a metering feeder, and 0.1 part of antioxidant 168 and 1010 part of antioxidant are added respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; at the same time, 30 parts of alkali-free glass fiber (commercial number T436H) is added into a side feeding system, and the glass fiber composite material is prepared by extrusion, cooling, grain cutting, uniform mixing and packaging. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Example 5

Preparation of (mono) polyester block copolymer

1.1 slurry preparation:

1) dicarboxylic acid (PTA) and diol (BDO, namely 1,4 butanediol) enter a slurry preparation tank U1 through a metering system respectively and are uniformly stirred to obtain slurry S1, wherein the PTA is 773G (G means gram, the same below), and the BDO is 520G.

2) The dicarboxylic acid PTA and R2 (alpha, omega-hydroxypropyl polydimethylsiloxane) used in the slurry 1) enter a slurry preparation tank U2 through a metering system respectively, and are uniformly stirred to be recorded as slurry S2, wherein the PTA is 154G, and the R2 is 80G.

1.2 catalyst preparation: adding 100G of dihydric alcohol (BDO) and 158.9G of catalyst C (tetrabutyl titanate) into a preparation tank U3, heating and boiling for 2-3 hours in a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 180 ℃, and transferring the prepared catalyst into a catalyst feeding tank after cooling.

1.3 esterification: and (3) pumping the slurry S1 in the slurry tank U1 into an esterification kettle E1 through a slurry pump, delivering the prepared catalyst C into the esterification kettle E1 through a gear pump, and carrying out esterification reaction under the action of the catalyst until no water is generated, so as to obtain the oligomer OM 1. The amount of the catalyst added was 0.05% based on the mass ratio C/S1 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate reaches 99.2 percent.

1.4 esterification: and (3) delivering the slurry S2 in the slurry tank U2 into an esterification kettle E2 through a slurry pump, delivering the prepared catalyst into the esterification kettle E2 through a gear pump, carrying out esterification reaction under the action of the catalyst until no water is generated, and generating an oligomer OM 2. The amount of the catalyst added was 0.05% based on the mass ratio C/S2 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate is 99 percent.

1.5 pre-polycondensation reaction: the oligomers in esterification kettles E1 and E2 are respectively fed into the pre-polycondensation kettle in proportion, wherein the proportion OM2/(OM1+ OM2) of OM2 in esterification kettle E2 is 30%. The initial polycondensation process in the esterification reaction is continuously carried out in a pre-polycondensation kettle, the pre-polycondensation reaction temperature is 245 ℃, the vacuum degree is-2 KPa, the reaction time is 40min, a low molecular weight polyester copolymer is generated, and the pre-polycondensation product enters a polycondensation reactor through a pre-polycondensation discharge pump, a pre-polycondensation discharge filter and a pre-polycondensation discharge cooler.

1.6 polycondensation reaction: and (3) feeding the pre-polycondensation product into a polycondensation reactor from the pre-polycondensation unit, and continuously reacting the prepolymer, wherein the polycondensation reaction temperature is 248 ℃, the vacuum degree is 120Pa, and the reaction time is 200min, so that the high-molecular-weight polyester block copolymer is generated. The polycondensation product enters a granulator system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter and a polycondensation discharge distribution valve. Cooling and pelletizing to obtain the high molecular weight polyester block copolymer product.

1.7 solid-phase tackifying reaction: the polyester block copolymer particles obtained by the polycondensation reaction are sent into a tackifying kettle, and solid phase reaction is carried out at a set temperature under the vacuum state of 10Pa or the protection of inert gas, and the reaction time is 20 hours.

The intrinsic viscosity of the resulting polyester block copolymer was 0.89 dL/g. The temperature was set at 200 ℃.

Blending modification of (di) polyester block copolymer and glass fiber

69.8 parts by weight of polyester block copolymer is weighed and dried for 2 to 4 hours at the temperature of between 80 and 120 ℃, and the moisture content is controlled to be less than 0.05 percent. The dried polyester block copolymer is fed into a twin-screw extruder from a metering feeder, and 0.1 part of antioxidant 168 and 1010 part of antioxidant are added respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; at the same time, 30 parts of alkali-free glass fiber (commercial number T436H) is added into a side feeding system, and the glass fiber composite material is prepared by extrusion, cooling, grain cutting, uniform mixing and packaging. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Example 6

Preparation of (mono) polyester block copolymer

1.1 slurry preparation:

1) dicarboxylic acid (PTA) and diol (BDO, namely 1,4 butanediol) enter a slurry preparation tank U1 through a metering system respectively and are uniformly stirred to obtain slurry S1, wherein the PTA is 773G (G means gram, the same below), and the BDO is 520G.

2) The dicarboxylic acid PTA and R2 (alpha, omega-hydroxypropyl polydimethylsiloxane) used in the slurry 1) enter a slurry preparation tank U2 through a metering system respectively, and are uniformly stirred to be recorded as slurry S2, wherein the PTA is 154G, and the R2 is 80G.

1.2 catalyst preparation: adding 100G of dihydric alcohol (BDO) and 158.9G of catalyst C (tetrabutyl titanate) into a preparation tank U3, heating and boiling for 2-3 hours in a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 180 ℃, and transferring the prepared catalyst into a catalyst feeding tank after cooling.

1.3 esterification: and (3) pumping the slurry S1 in the slurry tank U1 into an esterification kettle E1 through a slurry pump, delivering the prepared catalyst C into the esterification kettle E1 through a gear pump, and carrying out esterification reaction under the action of the catalyst until no water is generated, so as to obtain the oligomer OM 1. The amount of the catalyst added was 0.05% based on the mass ratio C/S1 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate reaches 99.2 percent.

1.4 esterification: and (3) delivering the slurry S2 in the slurry tank U2 into an esterification kettle E2 through a slurry pump, delivering the prepared catalyst into the esterification kettle E2 through a gear pump, carrying out esterification reaction under the action of the catalyst until no water is generated, and generating an oligomer OM 2. The amount of the catalyst added was 0.05% based on the mass ratio C/S2 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate is 99 percent.

1.5 pre-polycondensation reaction: the oligomers in the esterification kettles E1 and E2 are respectively fed into the pre-polycondensation kettle in proportion, wherein the proportion OM2/(OM1+ OM2) of OM2 in the esterification kettle E2 is 40%. The initial polycondensation process in the esterification reaction is continuously carried out in a pre-polycondensation kettle, the pre-polycondensation reaction temperature is 245 ℃, the vacuum degree is-2 KPa, the reaction time is 40min, a low molecular weight polyester copolymer is generated, and the pre-polycondensation product enters a polycondensation reactor through a pre-polycondensation discharge pump, a pre-polycondensation discharge filter and a pre-polycondensation discharge cooler.

1.6 polycondensation reaction: and (3) feeding the pre-polycondensation product into a polycondensation reactor from the pre-polycondensation unit, and continuously reacting the prepolymer, wherein the polycondensation reaction temperature is 248 ℃, the vacuum degree is 120Pa, and the reaction time is 200min, so that the high-molecular-weight polyester block copolymer is generated. The polycondensation product enters a granulator system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter and a polycondensation discharge distribution valve. Cooling and pelletizing to obtain the high molecular weight polyester block copolymer product.

1.7 solid-phase tackifying reaction: the polyester block copolymer particles obtained by the polycondensation reaction are sent into a tackifying kettle, and solid phase reaction is carried out at a set temperature under the vacuum state of 10Pa or the protection of inert gas, and the reaction time is 20 hours.

The intrinsic viscosity of the resulting polyester block copolymer was 0.87 dL/g. The temperature was set at 200 ℃.

Blending modification of (di) polyester block copolymer and glass fiber

69.8 parts by weight of polyester block copolymer is weighed and dried for 2 to 4 hours at the temperature of between 80 and 120 ℃, and the moisture content is controlled to be less than 0.05 percent. The dried polyester block copolymer is fed into a twin-screw extruder from a metering feeder, and 0.1 part of antioxidant 168 and 1010 part of antioxidant are added respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; at the same time, 30 parts of alkali-free glass fiber (commercial number T436H) is added into a side feeding system, and the glass fiber composite material is prepared by extrusion, cooling, grain cutting, uniform mixing and packaging. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Example 7

Preparation of (mono) polyester block copolymer

1.1 slurry preparation:

1) terephthalic Acid (PTA) and 1, 4-Cyclohexanedimethanol (CHDM) respectively enter a slurry preparation tank U1 through a metering system, are uniformly stirred, and are marked as slurry S1, wherein PTA is 773G, and CHDM is 670G.

2) Feeding dicarboxylic acid PTA and alpha, omega-hydroxypropyl polydimethylsiloxane used in the slurry 1) into a slurry preparation tank U2 through a metering system respectively, and uniformly stirring to obtain slurry S2, wherein the PTA is 77G, and the alpha, omega-hydroxypropyl polydimethylsiloxane is 40G.

1.2 catalyst preparation: adding 128.89G of 1, 4-Cyclohexanedimethanol (CHDM) and 158.9G of catalyst C (tetrabutyl titanate) into a preparation tank U3, slowly heating to 200 ℃, heating and boiling for 2-3 hours in a vacuum state, wherein the vacuum degree is 20-30KPa, and transferring the prepared catalyst into a catalyst feeding tank after cooling.

1.3 esterification: and (3) delivering the slurry S1 in the slurry tank U1 into an esterification kettle E1 through a slurry pump, delivering the prepared catalyst C into the esterification kettle E1 through a gear pump, and carrying out esterification reaction under the action of the catalyst until no water is generated, so as to obtain the oligomer OM 1. The amount of the catalyst added was 0.05% based on the mass ratio C/S1 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 280 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate reaches 99.1 percent.

1.4 esterification: and (3) delivering the slurry S2 in the slurry tank U2 into an esterification kettle E2 through a slurry pump, delivering the prepared catalyst into the esterification kettle E2 through a gear pump, carrying out esterification reaction under the action of the catalyst until no water is generated, and generating an oligomer OM 2. The amount of the catalyst added was 0.05% based on the mass ratio C/S2 of the slurry. The reaction conditions of the esterification kettle are as follows: the temperature is 245 ℃, the vacuum degree is 42KPa, the reaction time is 2 hours, and the esterification rate is 99 percent.

1.5 pre-polycondensation reaction: the oligomers in the esterification kettles E1 and E2 are respectively fed into the pre-polycondensation kettle in proportion, wherein the proportion OM2/(OM1+ OM2) added by OM2 in the esterification kettle E2 is 10%. The initial polycondensation process in the esterification reaction is continuously carried out in a pre-polycondensation kettle, the pre-polycondensation reaction temperature is 300 ℃, the vacuum degree is-2 KPa, the reaction time is 40min, a low molecular weight polyester copolymer is generated, and the pre-polycondensation product enters a polycondensation reactor through a pre-polycondensation discharge pump, a pre-polycondensation discharge filter and a pre-polycondensation discharge cooler.

1.6 polycondensation reaction: and (3) feeding the pre-polycondensation product into a polycondensation reactor from the pre-polycondensation unit, and continuously reacting the prepolymer, wherein the polycondensation reaction temperature is 300 ℃, the vacuum degree is 120Pa, and the reaction time is 200min, so that the high-molecular-weight polyester block copolymer is generated. The polycondensation product enters a granulator system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter and a polycondensation discharge distribution valve. Cooling and pelletizing to obtain the high molecular weight polyester block copolymer product. The intrinsic viscosity of the resulting polyester block copolymer was 0.56 dL/g.

1.7 solid-phase tackifying reaction: the polyester block copolymer particles obtained by the polycondensation reaction are sent into a tackifying kettle, and solid phase reaction is carried out at a set temperature under the vacuum state of 10Pa or the protection of inert gas, and the reaction time is 20 hours.

The intrinsic viscosity of the resulting polyester block copolymer was 0.82 dL/g. The temperature was set at 260 ℃.

Blending modification of (di) polyester block copolymer and glass fiber

69.8 parts by weight of polyester block copolymer is weighed and dried for 2 to 4 hours at the temperature of between 80 and 120 ℃, and the moisture content is controlled to be less than 0.05 percent. The dried polyester block copolymer is fed into a twin-screw extruder from a metering feeder, and 0.1 part of antioxidant 168 and 1010 part of antioxidant are added respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 260-300 ℃, and the screw rotating speed is 320 rpm; at the same time, 30 parts of glass fiber (commercial number T436H) is added into a side feeding system, and the glass fiber composite material is prepared by extrusion, cooling, grain cutting, uniform mixing and packaging. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Example 8

Preparation of (mono) polyester block copolymer

The polyester block copolymer was prepared according to the procedure described in example 2.

Blending modification of (di) polyester block copolymer and basalt fiber

69.8 parts by weight of polyester block copolymer is weighed and dried for 2 to 4 hours at the temperature of between 80 and 120 ℃, and the moisture content is controlled to be less than 0.05 percent. The dried polyester block copolymer is fed into a twin-screw extruder from a metering feeder, and 0.1 part of antioxidant 168 and 1010 part of antioxidant are added respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; and simultaneously adding 30 parts of basalt fiber (commercial brand BFCS-13-6) into a side feeding system, and performing extrusion, cooling, grain cutting, uniform mixing and packaging to obtain the basalt fiber. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Comparative example 1

One, ordinary PBT resin without silicon unit is adopted as comparison.

Blending modification of (II) common PBT resin and glass fiber

Weighing 69.8 parts by weight of PBT resin (Nantong star PBT1090) and drying at 80-120 ℃ for 2-4 hours, wherein the water content is controlled to be less than 0.05%; and (3) feeding the dried PBT resin into a double-screw extruder from a metering feeder, and adding 0.1 part of antioxidant 168 and 1010 respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; at the same time, 30 parts of glass fiber (commercial number T436H) is added into a side feeding system, and the glass fiber composite material is prepared by extrusion, cooling, grain cutting, uniform mixing and packaging. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Comparative example 2

One, ordinary PBT resin without silicon unit is adopted as comparison.

Blending modification of (II) common PBT resin and basalt fiber

Weighing 69.8 parts by weight of PBT resin (Nantong star PBT1090) and drying at 80-120 ℃ for 2-4 hours, wherein the water content is controlled to be less than 0.05%; and (3) feeding the dried PBT resin particles into a double-screw extruder from a metering feeder, and adding 0.1 part of antioxidant 168 and 1010 respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; and simultaneously adding 30 parts of basalt fiber (commercial brand BFCS-13-6) into a side feeding system, and performing extrusion, cooling, grain cutting, uniform mixing and packaging to obtain the basalt fiber. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Comparative example 3

One, ordinary PCT resin, without silicon units, was used for comparison.

Blending modification of (II) common PCT resin and glass fiber

Weighing 69.8 parts by weight of PCT resin (SK3502) and drying at 80-120 deg.C for 2-4 hr, and controlling water content to be less than 0.05%; dried PCT resin particles are fed into a double-screw extruder from a metering feeder, and 0.1 part of antioxidant 168 and 0.1 part of antioxidant 1010 are added respectively. The length-diameter ratio of the double-screw extruder is 40:1, the extrusion temperature is 170-260 ℃, and the screw rotating speed is 320 rpm; at the same time, 30 parts of glass fiber (commercial number T436H) is added into a side feeding system, and the glass fiber composite material is prepared by extrusion, cooling, grain cutting, uniform mixing and packaging. The resulting material was dried at 120 ℃ for 4h and then prepared by an injection molding machine into standard bars for testing.

Test results

TABLE 1 test data for examples 1-6 and comparative example 1

⁽¹⁾Data were aged at 85 ℃ and 85% humidity after 1000 hours of humid heat aging.

TABLE 2 Experimental data for examples 7-8 and comparative examples 2-3

Performance testing	Example 7	Comparative example 3	Example 8	Comparative example 2
					Intrinsic viscosity dL/g of resin	0.82	0.75	0.90	0.90
Bending strength MPa	176	178	228	235
					Bending strain%	8	4	9	3
Bending strength MPa(2)	169	162	196	198
					Bending strain%(2)	5	0.5	6	1
Impact ofStrength KJ/m2(23℃)	9	6	10	6
					Impact strength KJ/m2(-40℃)	6	3	7	3
Surface polarity (dyne value)	34	38	36	43
					Insertion and extraction force test	32	21	40	24
Insertion and extraction force test(2)	16	2	20	2

⁽²⁾Data were aged at 85 ℃ and 85% humidity after 1000 hours of humid heat aging.

The following results were obtained from the test data of the examples and comparative examples:

(1) the composite material prepared by the polyester block copolymer containing the silicon unit and the inorganic fiber is superior to a common polyester inorganic fiber reinforced material in bending strain, notch impact strength and low-temperature notch impact strength.

(2) Because the polyester block copolymer containing silicon units is adopted, the polarity of the polyester composite material is obviously reduced, the performance of the material after humid and hot aging is improved, and the application field of the material is expanded.

From the above results, it is clear that the polyester composite material provided by the present invention has excellent insertion and extraction resistance, hydrolysis resistance and low temperature resistance.

Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A polyester composite material, characterized by being prepared from A, B, C comprising the following parts by weight,

(I) a is a polyester block copolymer containing silicon units, the content of the polyester block copolymer is 30 weight parts < A <100 weight parts, and the structural formula is shown as follows:

-M-N- (formula α)

In the formula alpha, M is one or more of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate and polybutylene naphthalate;

the structural formula of N is shown as follows:

in the formula beta, R₃And R₄Is one of methyl, ethyl or phenyl; r₅Is composed of

Or

(II) B is an inorganic fiber, the content of which is 0 weight part < B <50.1 weight parts;

(III) C is an additive, and the content of the additive is more than or equal to 0 weight part and less than 10 weight parts.

2. The polyester composite of claim 1, wherein the intrinsic viscosity of the polyester block copolymer is from 0.6 to 2.0dL/g, preferably from 0.70 to 1.33dL/g, and more preferably from 0.78 to 1.10 dL/g.

3. The polyester composite according to claim 1 or 2, wherein the content of M in the polyester block copolymer is 0 parts by weight < M ≦ 99 parts by weight, preferably the content of M is 50 parts by weight < M ≦ 95 parts by weight, more preferably the content of M is 80 parts by weight < M ≦ 95 parts by weight;

and/or the N is present in an amount of 0 parts by weight < N.ltoreq.60 parts by weight, preferably in an amount of 1 part by weight < N.ltoreq.40 parts by weight, more preferably in an amount of 3 parts by weight < N.ltoreq.20 parts by weight.

4. The polyester composite according to any one of claims 1 to 3, wherein R in N is R when M is PET, PTT, PBT or PCT₅Has the structural formula

When M is PEN or PBN, R in N₅Has the structural formula

5. The polyester composite according to any one of claims 1 to 4, wherein the inorganic fibers are selected from one or more of glass fibers, basalt fibers, quartz fibers, ceramic fibers, boron fibers, silicon nitride fibers or carbon fibers, preferably glass fibers, basalt fibers or quartz fibers, most preferably glass fibers;

and/or the additive is selected from one or more of an antioxidant, a heat stabilizer, an ultraviolet light stabilizer, a coloring agent, an anti-hydrolysis agent, a mold release agent, a lubricant, a plasticizer, a dispersing aid, a reinforcing filler, a flow modifier, a chain extender and a flame retardant.

6. A method for preparing a polyester composite material, comprising:

(1) introducing polysilane molecules into a polyester molecular structure, and obtaining a polyester block copolymer by a copolymerization method;

(2) and then carrying out inorganic fiber reinforcement modification on the polyester block copolymer to obtain the polyester composite material in a blending mode.

7. The method for preparing a polyester composite material according to claim 6, wherein the step (1) comprises:

s1, carrying out esterification reaction on dibasic acid and dihydric alcohol to generate an intermediate product M;

s2, the dibasic acid which is the same as the dibasic acid S1 and the compound shown in the formula (III) are subjected to esterification reaction to generate an intermediate product N;

the compound of formula (III) has the following structure:

s3, mixing M and N for pre-polycondensation reaction;

s4, continuing to perform polycondensation reaction to generate a polyester block copolymer A containing silicon units;

preferably, in S1, the dibasic acid is terephthalic acid or terephthalic acid;

and/or the dihydric alcohol is ethylene glycol, propylene glycol, butanediol or 1, 4-cyclohexanedimethanol;

and/or the molar ratio of the dibasic acid to the dihydric alcohol is 1:1-1: 1.5;

and/or the compound shown in the formula (III) is selected from one or more of alpha, omega-dihydroxyethyl polydimethylsiloxane, alpha, omega-dihydroxyethyl polydiethylsiloxane, alpha, omega-dihydroxyethyl polymethylphenylsiloxane and alpha, omega-dihydroxyethyl polydiphenylsiloxane;

and/or the molar ratio of the dibasic acid to the compound shown in the formula (III) is 1:1.2-1: 1.5;

and/or, the reaction in the S1/S2 is carried out under the action of a catalyst; the catalyst is selected from one or more of germanium oxide, manganese acetate, zinc acetate, tetrabutyl titanate, antimony trioxide, ethylene glycol antimony and ethylene glycol titanium; the mass of the catalyst accounts for 0.01-0.1% of the total mass of the reaction raw materials;

and/or, in the above S1, a mixed system of a catalyst and a glycol is used, the preparation method of the mixed system comprising: placing the dihydric alcohol and the catalyst into a reaction kettle according to a ratio, heating and boiling under a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 170-200 ℃, and cooling; wherein the molar ratio of the dihydric alcohol to the catalyst is 1:3-1: 6;

and/or, in the above S1/S2, the esterification reaction conditions are: the temperature is 160-245 ℃, and the vacuum degree is 40-45 KPa;

and/or, in the above S3, the pre-polycondensation reaction conditions are: the temperature is 180 ℃ and 310 ℃, the vacuum degree is 1.5-2.5KPa, and the reaction time is 30-60 min;

and/or, in the above S4, the polycondensation reaction conditions are: the temperature is 180-;

and/or, carrying out solid-phase tackifying reaction on the prepared polyester block copolymer; the temperature of the solid phase tackifying reaction is 100-260 ℃.

8. The method for preparing the polyester composite material according to claim 7, wherein the preparation of the polyester block copolymer comprises the following specific steps:

k1: preparation of slurry

Placing dicarboxylic acid and dihydric alcohol in a container, and uniformly stirring to obtain a mixed material 1; wherein the molar ratio of the dicarboxylic acid to the diol is 1:1-1: 1.5;

placing the dibasic acid and the compound shown in the formula (III) in a container, and uniformly stirring to obtain a mixed material 2; wherein the molar ratio of the dibasic acid to the compound shown in the formula (III) is 1:1.2-1: 1.5;

k2: catalyst formulation

Adding the dihydric alcohol and the catalyst into a container according to the molar ratio of 1:3-1:6, heating and boiling for 2-4 hours under a vacuum state, wherein the vacuum degree is 20-30KPa, the temperature is 170-200 ℃, and cooling to obtain a catalyst mixed system;

k3: esterification reaction

Placing the mixed material 1 in a reaction kettle, adding a catalyst mixed system for esterification reaction until no water is generated, and generating oligomer OM 1; wherein the mass ratio of the added catalyst to the mixed material 1 is 0.01-0.1%; the esterification reaction conditions are as follows: the temperature is 160-245 ℃, the vacuum degree is 40-45KPa, and the reaction time is 1-3 hours;

placing the mixed material 2 in a reaction kettle, adding a catalyst mixed system for esterification reaction until no water is generated; generating oligomer OM2, namely the compound shown in the formula (beta);

wherein the mass ratio of the added catalyst to the mixed material 2 is 0.01-0.1%; the esterification reaction conditions are as follows: the temperature is 160-245 ℃, the vacuum degree is 40-45KPa, and the reaction time is 1-3 hours;

k4: prepolycondensation reaction

Placing oligomer OM1 and oligomer OM2 in a reaction kettle, and carrying out pre-polycondensation reaction to generate a low-molecular-weight polyester copolymer; wherein the proportion of the mass of the oligomer OM1 to the sum of the masses of the oligomer OM1 and the oligomer OM2 is 0.1-50%; the pre-polycondensation reaction conditions are as follows: the temperature is 180 ℃ and 310 ℃, the vacuum degree is 1.5-2.5KPa, and the reaction time is 30-60 min;

k5: polycondensation reaction

Putting the pre-polycondensation product obtained in the step K4 into a reaction kettle, and carrying out polycondensation reaction to generate a compound shown in the formula (I); the polycondensation reaction conditions are as follows: the temperature is 180-; the intrinsic viscosity of the obtained polyester block copolymer is 0.5-1.0 dL/g;

k6: solid phase tackifying reaction

Feeding the polyester block copolymer particles obtained by the polycondensation reaction into a tackifying kettle, carrying out solid phase reaction at a set temperature of 100 ℃ and 260 ℃ under the vacuum state of 3-100Pa or the inert gas protection state with the flow rate of inert gas of 0.5-5L/[ min. KG tackifying particles, and the reaction time of 4-36 hours to obtain the polyester block copolymer;

preferably, the reaction conditions are optimized for the characteristics of the starting materials:

when the dicarboxylic acid is 2, 6-naphthalenedicarboxylic acid in the step K1, the pre-polycondensation reaction temperature ranges from 250-310 ℃, the polycondensation reaction temperature ranges from 250-310 ℃, and the solid-phase tackifying reaction temperature ranges from 200-240 ℃;

when the dicarboxylic acid is terephthalic acid and the diol is 1, 4-cyclohexanedimethanol in the step K1, the pre-polycondensation reaction temperature ranges from 280-310 ℃, the polycondensation reaction temperature ranges from 280-310 ℃, and the solid phase tackifying reaction temperature ranges from 240-260 ℃;

when the dicarboxylic acid is terephthalic acid, the diol is one other than 1, 4-cyclohexanedimethanol or a mixture of two or more diols in the step K1, the pre-polycondensation reaction temperature ranges from 200-250 ℃, the polycondensation reaction temperature ranges from 200-250 ℃, and the solid phase tackifying reaction temperature ranges from 180-220 ℃.

9. The preparation method of the polyester composite material according to claim 6, wherein the step (2) specifically comprises:

s5 drying: drying the obtained polyester block copolymer and inorganic fiber at 80-120 deg.C for 2-4 hr, and drying the rest additives at corresponding temperature;

s6, batching: weighing the polyester block copolymer A, the inorganic fiber B and the additive C according to a set proportion to meet the requirement that A + B + C is 100;

s7 extrusion: adding the materials into a double-screw extruder, carrying out melt extrusion, bracing, cooling and granulation;

preferably, the extrusion equipment adopts a double-screw extruder, and the length-diameter ratio of the extruder is 32-48: 1;

and/or the temperature of the extrusion is 170-300 ℃;

and/or the screw rotating speed during the extrusion is 180-900 rpm;

and/or the polyester block copolymer in the step S6 is one or more of PET containing a silicon unit, PTT containing a silicon unit, PBT containing a silicon unit, PCT containing a silicon unit, PEN containing a silicon unit and PBN containing a silicon unit, preferably PBT containing a silicon unit;

and/or, the inorganic fiber in the step S6 is selected from one or more of glass fiber, basalt fiber, quartz fiber, ceramic fiber, boron fiber, silicon nitride fiber and carbon fiber, preferably glass fiber, basalt fiber or quartz fiber, and optimally glass fiber;

and/or, the alkali content in the glass fiber is not more than 13 percent in terms of the content of sodium oxide, more preferably, the alkali content of the glass fiber is not more than 8 percent, and the most preferably, the alkali content of the glass fiber is less than 2 percent;

and/or, the additive in the step S6 is selected from one or more of antioxidants, heat stabilizers, ultraviolet light stabilizers, coloring agents containing dyes and pigments, anti-hydrolysis agents, mold release agents, lubricants, plasticizers, dispersing aids, reinforcing fillers, flow modifiers, chain extenders and flame retardants.

10. Use of the polyester composite according to any one of claims 1 to 5 in the fields of electronics, automotive, lighting, machinery, spinning, communications, films or instrumentation.