CN113667285B - High-toughness plastic and preparation method thereof - Google Patents
High-toughness plastic and preparation method thereof Download PDFInfo
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Abstract
The application relates to a high-toughness plastic and a preparation method thereof, wherein the high-toughness plastic comprises the following components in parts by weight: 87.4-91.4 parts of PBT; 0.3-0.5 part of a lubricant; 0.3-0.5 part of antioxidant; 8-12 parts of modified glass fiber; the preparation steps of the modified glass fiber are as follows: a. pretreatment: preheating glass fiber, carrying out vacuum freeze drying, sequentially carrying out heating reaction on the glass fiber and hydrogen peroxide and a silane coupling agent, and filtering and drying to obtain silane modified glass fiber; b. modification treatment: carrying out vacuum heating reaction on the silane modified glass fiber and the modified sol to prepare modified glass fiber; the modified sol consists of mixed resin, modified filler and surfactant, wherein the mixed resin consists of carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin. The plastic shell that this application was made has the advantage of high tenacity and high moment of torsion concurrently.
Description
Technical Field
The application relates to the technical field of polybutylene terephthalate, in particular to high-toughness plastic and a preparation method thereof.
Background
Polybutylene terephthalate, also known as PBT, is a crystalline thermoplastic polyester that is milky translucent to opaque. It is one of five engineering plastics, has the advantages of high heat resistance, toughness, fatigue resistance, self lubrication, low friction coefficient, weather resistance and low water absorption, therefore, the composite material is often used in a plurality of fields such as electric appliances, automobiles, aircraft manufacturing, communication, household appliances, transportation and the like.
The PBT resin in the related art is mostly used as a compound of mixed resin, namely modified by various additives or blended with other resins to obtain good comprehensive properties such as heat resistance, flame retardance, electric insulation and the like and good processability. The PBT filled and modified by 15-25% of glass fiber is taken as an example, has strong thermal stability and extrusion deformation resistance, and can be used for manufacturing electronic part shells with requirements on working conditions at 140 ℃ for a long time and high dimensional stability.
However, the molding shrinkage of the glass fiber reinforced and modified PBT resin in the above ratio is large, that is, the longitudinal shrinkage and the transverse shrinkage of the product are not consistent, the shell of the product is easily warped, the torque is low, and when the ratio of the glass fiber is reduced, the high toughness of the PBT resin cannot be guaranteed. Accordingly, the present application provides a plastic that combines high toughness and high torque.
Disclosure of Invention
In order to enable the plastic to have the advantages of high toughness and high torque, the application provides the high-toughness plastic and the preparation method thereof.
In a first aspect, the present application provides a high toughness plastic, which adopts the following technical scheme:
a high-toughness plastic comprises the following components in parts by weight:
87.4-91.4 parts of PBT;
0.3-0.5 part of a lubricant;
0.3-0.5 part of antioxidant;
8-13 parts of modified glass fiber;
the preparation steps of the modified glass fiber are as follows:
a. pretreatment: preheating glass fiber, performing vacuum freeze drying on the glass fiber, mixing the glass fiber with hydrogen peroxide, heating the mixture to 110-120 ℃, refluxing the mixture for 1-2 hours, adding a silane coupling agent, heating the mixture to 90-100 ℃, continuously reacting for 3-6 hours, and filtering and drying the mixture to obtain pre-modified glass fiber;
b. modification treatment: pre-modified glass fiber and modified sol are mixed according to the weight ratio of 1: (2-5) heating and reacting for 2-3h at 90-120 ℃ under vacuum condition to obtain modified glass fiber;
the modified sol consists of mixed resin, modified filler and surfactant, wherein the mixed resin consists of carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin.
By adopting the technical scheme, the glass fiber after preheating and freeze drying treatment has a large number of fine cracks on the surface layer fiber, the subsequent reaction of the glass fiber and hydrogen peroxide is facilitated through the capillary action of the cracks, the surface layer bonding capability of the glass fiber is enhanced after the heating reflux reaction, and the presumed reason is probably that hydroxylated glass fiber is formed, and then the subsequent reaction with a silane coupling agent ensures stronger bonding effect of alkyl bonding groups, besides the modification of the surface of the glass fiber, the glass fiber can be crosslinked with partial hydroxylated glass fiber, and then the bonding force on the surface of the pre-modified glass fiber is endowed.
The pre-modified glass fiber can be stably combined with mixed resin under the action of a surfactant, and a modified adhesive layer is formed by coating the surface layer of the pre-modified glass fiber, wherein N, N-dimethylformamide can be used as a solvent and a blending agent to promote mutual grafting and crosslinking among carboxyl-terminated hyperbranched polyester, epoxy resin and the surface of the pre-modified glass fiber, so that a certain synergistic effect is achieved, the overall excellent plasticity and anti-warping capability of the modified adhesive layer are endowed, the influence of glass fiber shrinkage on plastic torque is remarkably reduced, and the modified glass fiber and the plastic are endowed with excellent toughness through combined filling of modified fillers.
Preferably, the specific processing steps in a are as follows: preheating glass fiber to 80-100 ℃, then cooling to 0 ℃, and after vacuum drying, mixing the glass fiber with hydrogen peroxide according to the weight ratio of 1: (2-3) mixing, heating to 110-120 ℃, refluxing for 2-4h, and then adding a silane coupling agent, wherein the weight ratio of the silane coupling agent to the glass fiber is 1: (8-12), heating to 90-100 ℃, continuing to react for 3-6h, and after the reaction is finished, filtering and drying to obtain the silane modified glass fiber.
By adopting the technical scheme, the surface layer fiber of the glass fiber after the preheating and freeze drying treatment has more dense and fine cracks, the capillary phenomenon is more obvious, the reaction of the glass fiber and hydrogen peroxide is more obvious, the binding force on the surface of the glass fiber is greatly improved, the subsequent reaction with a silane coupling agent is facilitated, the binding effect of an alkyl binding group is ensured, and the excellent binding force and the binding effect on the surface of the pre-modified glass fiber are further endowed.
Preferably, the modified sol is prepared by mixing a mixed resin, a modified filler and a surfactant according to a weight ratio of 1: (0.2-0.3): (0.03-0.05).
By adopting the technical scheme, the coating combination effect of the modified sol and the pre-modified glass fiber is better under the above proportion, the modified filler is filled more tightly, the excellent toughness and anti-warping capability of the modified glue layer are given by the characteristics of the modified sol and the pre-modified glass fiber, the toughening and reinforcing effects of the modified glass fiber on the plastic are further ensured, and the plastic has the advantages of high toughness and high torque.
Preferably, the mixed resin is prepared from carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin according to the weight ratio of 1: (0.8-1.2): (0.2-0.3).
By adopting the technical scheme, the mixed resin in the proportion has a good synergistic effect, namely, the carboxyl-terminated hyperbranched polyester and the epoxy resin can be fully grafted and crosslinked with the surface layer of the pre-modified glass fiber under the blending action of N, N-dimethylformamide, and the modified glue layer has high toughness and anti-warping capability while being combined stably, so that the high toughness and high torque of the modified glass fiber are ensured.
Preferably, the modified filler is graphene, nano diatomite and nano silica according to a weight ratio of 1: (0.2-0.3): (0.5-0.8).
By adopting the technical scheme, the modified glass fiber with the components and the proportion can be endowed with excellent toughness and torque through the characteristics and the compounding effect of the nano material, and can be fully dispersed on a modified adhesive layer and is not easy to peel.
Preferably, the surfactant is composed of one or more of diethylenetriamine, sodium lauryl sulfate and glyceryl stearate.
By adopting the technical scheme, the surfactant with the components can improve the bonding performance of the surface of the pre-modified glass fiber and form a bonding interface which is easy to crosslink between the surface of the pre-modified glass fiber and the mixed resin, so that the modification effect of the modified glass fiber is guaranteed.
Preferably, the silane coupling agent is one or more of vinyltriethoxysilane, methacryloxypropyltrimethoxysilane and aminosilanes.
By adopting the technical scheme, the silane coupling agent of the components can be fully grafted or crosslinked with the surface of the glass fiber and part of the hydroxylated glass fiber, so that the pre-modified glass fiber is endowed with excellent binding force, and the subsequent modification treatment is facilitated.
Preferably, the lubricant is prepared from ethylene bis stearamide, zinc stearate and sorbitol in a weight ratio of 1: (0.5-0.8): (2-3).
By adopting the technical scheme, the lubricating agent prepared from the components and the proportion has a sufficient lubricating effect between the PBT and the modified glass fiber, so that the modified glass fiber can be sufficiently dispersed and combined between the PBT, and the plastic is endowed with excellent toughness and torque.
Preferably, the antioxidant is prepared from thiobisphenol, benzophenone and p-phenylenediamine in a weight ratio of 1: (0.1-0.2): (0.8-1.2).
By adopting the technical scheme, the antioxidant prepared from the components and the proportion has a certain compounding effect, can effectively inhibit the generation of free radicals in a polymer system, further achieves the process of delaying or inhibiting the oxidation of the polymer, and has the advantages of difficult aging and long service life.
In a second aspect, the present application provides a method for preparing a high-toughness plastic, which adopts the following technical scheme:
a preparation method of high-toughness plastic comprises the following steps:
s1, preparing materials: firstly, mixing the modified glass fiber, PBT, a lubricant and an antioxidant according to corresponding parts by weight to prepare mixed powder;
s2, pressing and sintering: adding the mixed powder into a mold, and heating and sintering after pressure application, exhaust and pressure maintaining treatment to prepare a sintered material;
s3, cooling: and cooling the sintered material to room temperature, and taking out the sintered material from the die to obtain the high-toughness plastic.
By adopting the technical scheme, the preparation process is simple, various conditions are easy to achieve, and the regulation and control are easy, so that the preparation method is suitable for industrial production, and the plastic with high toughness and high torque can be prepared in a large scale.
In summary, the present application has the following beneficial effects:
1. according to the application, the surface of the pre-modified glass fiber is endowed with excellent cohesive force through the pretreatment of the glass fiber, then in the subsequent modification treatment process with the modified sol, the mixed resin and the modified filler can be stably combined and coated on the surface layer of the pre-modified glass fiber to form a modified glue layer, and the modified glass fiber and the plastic are endowed with the advantages of high toughness and high torque through the characteristics and the compounding effect of the material;
2. according to the application, the mixed resin with a specific ratio guarantees full grafting and crosslinking of the modified adhesive layer and the surface layer of the pre-modified glass fiber, the synergistic effect of the three is good, and the formed modified adhesive layer has strong warping resistance and toughness, so that the high toughness and high torque of the modified glass fiber are guaranteed;
3. the preparation steps are simple, all conditions are easy to control and achieve, and the prepared plastic is stable and uniform in performance, has excellent high toughness and high torque, and is suitable for industrial mass production.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the examples of the present application are commercially available, except for the following specific descriptions:
PBT GX211, purchased from China petrochemical certified chemical fibers Co., ltd;
glass fiber, brand HGM436S, purchased from Mount Taishan glass fiber Co., ltd;
carboxyl-terminated hyperbranched polyester, the trademark HyPer C10, purchased from Wuhan hyperbranched resins technology, inc.;
n, N-dimethylformamide, CAS 68-12-2;
epoxy resin, CAS 24969-06-0;
graphene, CAS 1034343-98-0;
1000 mesh, CAS 91053-39-3, purchased from Yuanda Muscovitum, lingshu county;
nano silica, 1000 mesh, purchased from north Hessina nano materials science and technology limited;
aminosilane, trade name KH-792, CAS 1760-24-3, purchased from Longkai chemical Co., ltd, guangzhou.
Preparation example
Preparation example 1
A modified glass fiber is prepared by the following steps:
a. pretreatment: preheating glass fiber to 80 ℃, then cooling to 0 ℃, and after vacuum drying, mixing the glass fiber with hydrogen peroxide according to the weight ratio of 1:2, mixing, heating to 110 ℃, refluxing for 2 hours, and then adding a silane coupling agent, wherein the weight ratio of the silane coupling agent to the glass fiber is 1:8, heating to 90 ℃, continuing to react for 3 hours, and filtering and drying after the reaction is finished to obtain the silane modified glass fiber;
the silane coupling agent is vinyl triethoxysilane;
b. modification treatment: pre-modified glass fiber and modified sol are mixed according to the weight ratio of 1:2 heating and reacting for 2 hours at 90 ℃ under vacuum condition to obtain modified glass fiber;
the modified sol is prepared from mixed resin, modified filler and surfactant according to a weight ratio of 1:0.1:0.02 percent;
the mixed resin is prepared from carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin according to the weight ratio of 1:0.6: 0.1;
the modified filler is graphene, nano diatomite and nano silicon dioxide according to a weight ratio of 1:0.1: 0.3;
the surfactant is diethylenetriamine.
Preparation example 2
A modified glass fiber is distinguished from preparation example 1 in that the preparation conditions are as follows:
a. pretreatment: preheating glass fiber to 90 ℃, then cooling to 0 ℃, and after vacuum drying, mixing the glass fiber with hydrogen peroxide according to the weight ratio of 1:2.5, mixing, heating to 115 ℃, refluxing for 3h, and then adding a silane coupling agent, wherein the weight ratio of the silane coupling agent to the glass fiber is 1:10, heating to 95 ℃, continuing to react for 4.5 hours, and after the reaction is finished, filtering and drying to obtain the silane modified glass fiber;
b. modification treatment: pre-modified glass fiber and modified sol are mixed according to the weight ratio of 1:3.5 heating and reacting for 2.5h at 105 ℃ under vacuum condition to obtain the modified glass fiber.
Preparation example 3
A modified glass fiber is distinguished from preparation example 1 in that the preparation conditions are as follows:
a. pretreatment: preheating glass fiber to 100 ℃, then cooling to 0 ℃, and after vacuum drying, mixing the glass fiber with hydrogen peroxide according to the weight ratio of 1:3, mixing, heating to 120 ℃, refluxing for 4 hours, and adding a silane coupling agent, wherein the weight ratio of the silane coupling agent to the glass fiber is 1:12, heating to 100 ℃, continuing to react for 6 hours, and filtering and drying after the reaction is finished to obtain the silane modified glass fiber;
b. modification treatment: pre-modified glass fiber and modified sol are mixed according to the weight ratio of 1: and 5, heating and reacting for 3 hours at 120 ℃ under a vacuum condition to obtain the modified glass fiber.
Preparation example 4
A modified glass fiber, which is different from the preparation example 1 in that the modified sol in the step b is prepared by mixing a resin, a modified filler and a surfactant according to a weight ratio of 1:0.2:0.03 composition.
Preparation example 5
A modified glass fiber, which is different from the preparation example 1 in that the modified sol in the step b is prepared by mixing a resin, a modified filler and a surfactant according to a weight ratio of 1:0.25:0.04 percent.
Preparation example 6
A modified glass fiber, which is different from the preparation example 1 in that the modified sol in the step b is prepared by mixing a resin, a modified filler and a surfactant according to a weight ratio of 1:0.3:0.05 composition.
Preparation example 7
A modified glass fiber, which is different from the preparation example 1 in that the modified sol in the step b is prepared by mixing a resin, a modified filler and a surfactant according to a weight ratio of 1:0.4: 0.06.
Preparation example 8
The modified glass fiber is different from the preparation example 5 in that the mixed resin in the step b is prepared by mixing carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin according to the weight ratio of 1:0.8: 0.2.
Preparation example 9
A modified glass fiber, which is different from the preparation example 5 in that the mixed resin in the step b is prepared by mixing carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin according to the weight ratio of 1:1.0: 0.25.
Preparation example 10
A modified glass fiber, which is different from the preparation example 5 in that the mixed resin in the step b is prepared by mixing carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin according to the weight ratio of 1:1.2: 0.3.
Preparation example 11
The modified glass fiber is different from the preparation example 5 in that the mixed resin in the step b is prepared by mixing carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin according to the weight ratio of 1:1.4: 0.4.
Preparation example 12
The modified glass fiber is characterized in that the modified filler in the step b is prepared from graphene, nano kieselguhr and nano silicon dioxide in a weight ratio of 1:0.2: 0.5.
Preparation example 13
The modified glass fiber is characterized in that the modified filler in the step b is prepared from graphene, nano kieselguhr and nano silicon dioxide in a weight ratio of 1:0.25: 0.65.
Preparation example 14
The modified glass fiber is characterized in that the modified filler in the step b is prepared from graphene, nano kieselguhr and nano silicon dioxide in a weight ratio of 1:0.3: 0.8.
Preparation example 15
The modified glass fiber is characterized in that the modified filler in the step b is prepared from graphene, nano kieselguhr and nano silicon dioxide in a weight ratio of 1:0.4: 1.0.
Preparation example 16
A modified glass fiber, which is different from the preparation example 1 in that the silane coupling agent in the step a is methacryloxypropyltrimethoxysilane.
Preparation example 17
A modified glass fiber differing from preparation example 1 in that the silane coupling agent in a is a mixture of vinyltriethoxysilane and methacryloxypropyltrimethoxysilane in a weight ratio of 1:1.
Preparation example 18
A modified glass fiber, which is different from preparation example 1 in that the silane coupling agent in a is prepared from vinyltriethoxysilane, methacryloxypropyltrimethoxysilane and aminosilane in a weight ratio of 1:1: 1.
Preparation example 19
A modified glass fiber, which is different from preparation example 1 in that the surfactant in b is sodium lauryl sulfate.
Preparation example 20
A modified glass fiber, which is different from the preparation example 1 in that in the step b, the surfactant is prepared from diethylenetriamine and sodium dodecyl sulfate according to the weight ratio of 1:1.
Preparation example 21
A modified glass fiber, which is different from the preparation example 1 in that in the b, the surfactant is composed of diethylenetriamine, sodium dodecyl sulfate and glycerol stearate according to the weight ratio of 1:1: 1.
Examples
Example 1
A high-toughness plastic, the components and their corresponding weights are shown in Table 1, and is prepared by the following steps:
s1, preparing materials: heating the modified glass fiber, PBT, lubricant and antioxidant to 200 ℃, and mixing for 30min at a speed of 200r/min according to the corresponding weight to prepare mixed powder;
the modified glass fiber was obtained in preparation example 1;
s2, pressing and sintering: adding the mixed powder into a mold, applying pressure of 30Mpa, exhausting for 4 times, controlling pressure of 35Mpa, performing pressure maintaining treatment for 45min, heating to 200 ℃, sintering for 3h, heating to 240 ℃, and sintering for 6h to obtain a sintered material;
s3, cooling: cooling the sintered material to room temperature of 25 ℃, and taking out the sintered material from the die to obtain the high-toughness plastic;
the lubricant is ethylene bis stearamide;
the antioxidant is thiobisphenol.
Examples 2 to 6
A high toughness plastic differing from example 1 in that the components and their respective weights are shown in table 1.
TABLE 1 Components and their weights (kg) in examples 1-6
Examples 7 to 26
A high-toughness plastic is different from the plastic in example 1 in the use condition of the modified glass fiber, and the specific corresponding relation is shown in Table 2.
TABLE 2 comparison of the use of modified glass fibers in examples 7-26
Example 27
A high toughness plastic differing from example 1 in that the lubricant consists of ethylene bisstearamide, zinc stearate and sorbitol in a weight ratio of 1:0.5: 2.
Example 28
A high-toughness plastic differing from example 1 in that a lubricant is prepared from ethylene bisstearamide, zinc stearate and sorbitol in a weight ratio of 1:0.65: 2.5.
Example 29
A high-toughness plastic differing from example 1 in that a lubricant is prepared from ethylene bisstearamide, zinc stearate and sorbitol in a weight ratio of 1:0.8:3, the components are mixed.
Example 30
A high toughness plastic differing from example 1 in that the antioxidant is a mixture of thiobisphenol, benzophenone and p-phenylenediamine in a weight ratio of 1:0.1: 0.8.
Example 31
A high toughness plastic differing from example 1 in that the antioxidant is a mixture of thiobisphenol, benzophenone and p-phenylenediamine in a weight ratio of 1:0.15: 1.0.
Example 32
A high-toughness plastic differing from that of example 1 in that the antioxidant is a mixture of thiobisphenol, benzophenone and p-phenylenediamine in a weight ratio of 1:0.2: 1.2.
Comparative example
Comparative example 1
A high toughness plastic differing from example 1 in that the glass fibers were not modified.
Comparative example 2
A high toughness plastic differs from example 1 in that the glass fibers are not pretreated.
Comparative example 3
A high toughness plastic differing from example 1 in that the modified sol did not contain a modified filler.
Comparative example 4
A high-toughness plastic, which differs from example 1 in that the modified sol does not contain a mixed resin.
Comparative example 5
A high toughness plastic differing from example 10 in that the mixed resin did not contain carboxyl-terminated hyperbranched polyester.
Comparative example 6
A high-toughness plastic which differs from that in example 10 in that N, N-dimethylformamide is not contained in the mixed resin.
Comparative example 7
A high toughness plastic differing from example 10 in that the epoxy resin was not contained in the mixed resin.
Comparative example 8
A high toughness plastic differing from example 10 in that the mixed resin did not contain carboxyl-terminated hyperbranched polyester and N, N-dimethylformamide.
Comparative example 9
A high toughness plastic, which differs from example 10 in that the mixed resin does not contain carboxyl-terminated hyperbranched polyester and epoxy resin.
Comparative example 10
A high-toughness plastic which differs from that in example 10 in that N, N-dimethylformamide and an epoxy resin are not contained in the mixed resin.
Performance test
The high-toughness plastics obtained in examples 1 to 26 and comparative examples 1 to 10 were each selected as a test object, processed into a type I specimen having a thickness of 7mm, tested for tensile modulus of elasticity by a tensile tester of the classification standard B-2 in the E83 standard, measured three times, and the average value was recorded in Table 3, and the specific test procedure and the test standard were described in ASTM D638-03, "test method for tensile Properties of plastics".
The high toughness plastics obtained in examples 1 to 26 and comparative examples 1 to 10 were each selected as a test object, processed into a sample of 80mm x 10mm x 4mm, and then tested for flexural strength and flexural modulus at a test speed of 2mm/min, and the average values after three measurements were recorded in table 3, and the specific test procedures and test standards were referred to GB934-2008 "test standards for flexural properties of plastics" and astm d790-03 "standard test methods for flexural properties of unreinforced and reinforced plastics and electrical insulating materials".
TABLE 3 results of Performance testing
As can be seen by combining examples 1-6, comparative example 1 and Table 3, examples 1-6 all have tensile elastic moduli higher than 3500MPa, flexural strengths higher than 121MPa, and flexural moduli higher than 3000MPa.
Example 3 is the most preferred example, and has a tensile modulus of elasticity of 3856MPa, a flexural strength of 122.3MPa and a flexural modulus of 3015MPa. The modified glass fiber with the component proportion has the best synergistic effect with other components, and can endow the plastic with high toughness and high torque characteristic through the characteristics of the modified glass fiber.
In comparative example 1, since the glass fiber was not modified, the tensile modulus of elasticity was only 3328Mpa, the flexural strength was only 120.1Mpa, and the flexural modulus was only 2713Mpa, the plastic torque was greatly reduced, and warpage was likely to occur due to shrinkage of the glass fiber.
In conclusion, after the glass fiber with the proportion is modified, the influence of the shrinkage on the plastic torque is reduced, and meanwhile, the plastic is endowed with excellent toughness and anti-warping capability through the characteristics of the glass fiber and the combination of other components.
It can be seen from the combination of examples 1, 7-8, comparative example 2 and Table 3 that examples 7-8 all have tensile elastic modulus higher than 3700MPa, bending strength higher than 122MPa and bending modulus higher than 3100MPa.
Example 7 is the most preferred example with tensile modulus of elasticity up to 3784MPa, flexural strength of 122.2MPa and flexural modulus of 3256MPa. Therefore, the modified glass fiber prepared under the process conditions in preparation example 2 has strong plasticity and anti-warping capability, and can ensure high toughness and high torque of the plastic through the characteristics of the modified glass fiber.
In comparative example 2, since no pretreatment was performed during the modification of the glass fiber, the tensile modulus of elasticity was only 3434MPa, the flexural strength was only 119.1MPa, and the flexural modulus was only 2955MPa, the toughness and the torque of the plastic were reduced.
In conclusion, the glass fiber treated by the process conditions has the best modification effect, namely, the bonding force and the bonding effect on the surface of the modified glass fiber are optimal, so that the prepared modified glass fiber can be combined with other components, the influence on the torque of a shell is reduced, and meanwhile, the plastic is endowed with excellent toughness and anti-warping capability.
Combining examples 1, 9-12, and 3-4 and combining Table 3, it can be seen that examples 9-12 all have tensile moduli of elasticity greater than 3700MPa, flexural strengths greater than 122MPa, and flexural moduli greater than 3200MPa.
Example 10 is the most preferred example having a tensile modulus of elasticity of 3828MPa, a flexural strength of 122.3MPa and a flexural modulus of 3293MPa. It can be seen that the modified sol ratio in preparation example 5 is the optimum ratio.
In comparative examples 3-4, due to the lack of some components in the modified sol, the tensile elastic modulus is less than 3500MPa, the bending strength is less than 122MPa, the bending modulus is less than 3000MPa, and the toughness and the torque of the plastic are reduced to different degrees.
In summary, when the modified sol is prepared by mixing the resin, the modified filler and the surfactant according to the weight ratio of 1:0.25: when the composition is 0.04, the coating combination effect of the modified glass fiber and the pre-modified glass fiber is the best, the modified filler is filled most tightly, the modified glue layer is endowed with excellent toughness and anti-warping capability, and then the modified glass fiber can play a remarkable toughening and reinforcing effect on plastics and endow the plastics with the characteristics of high toughness and high torque.
Combining examples 5, 13-16, and 5-10 with Table 3, it can be seen that examples 13-16 all have tensile moduli of elasticity greater than 3800MPa, flexural strengths greater than 122MPa, and flexural moduli greater than 3300MPa.
Example 14 is the best example, the tensile elastic modulus can reach 3905Mpa, the bending strength is 122.5Mpa, and the bending modulus is 3359Mpa, thus the blending ratio of the mixed resin in preparation example 9 is the best blending ratio.
In comparative examples 5 to 10, the tensile modulus of elasticity of the mixed resin was less than 3600MPa, the flexural strength was less than 122MPa, the flexural modulus was less than 3100MPa, and the toughness and the torque of the modified glass fiber and the plastic were reduced to various degrees because three components were not used at the same time.
In summary, when the modified sol is prepared by mixing the resin, the modified filler and the surfactant according to the weight ratio of 1:0.25:0.04, wherein the mixed resin is prepared from carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin according to the weight ratio of 1:1:0.25, the synergistic effect of the carboxyl-terminated hyperbranched polyester and the epoxy resin is best, the carboxyl-terminated hyperbranched polyester and the epoxy resin can be fully grafted and crosslinked with the surface layer of the pre-modified glass fiber under the blending action of N, N-dimethylformamide, and the modified glue layer is stable in combination and has excellent toughness and warping resistance, so that the modified glass fiber and the plastic have the advantages of high toughness and high torque.
As can be seen by combining example 5, examples 17-20 and Table 3, examples 17-20 all had tensile moduli greater than 3800MPa, flexural strengths greater than 122MPa and flexural moduli greater than 3300MPa.
Example 18 is the best example, the tensile elastic modulus can reach 3866Mpa, the bending strength is 122.4Mpa, the bending modulus is 3326Mpa, and the proportion of the modified filler in preparation example 13 is the best proportion.
In summary, when the modified sol is prepared by mixing the resin, the modified filler and the surfactant according to the weight ratio of 1:0.25:0.04, wherein the modified filler is prepared from graphene, nano diatomite and nano silicon dioxide in a weight ratio of 1:0.25: when the glass fiber is 0.65, the compounding effect of the components is optimal, and the toughness and the anti-warping performance of the modified glass fiber can be guaranteed through the self characteristics of the nano material and the dispersive combination of the nano material and the modified glue layer.
It can be seen from the combination of example 5, examples 21-23 and Table 3 that examples 21-23 all have tensile elastic modulus higher than 3850MPa, bending strength higher than 122MPa and bending modulus higher than 3300MPa.
Example 22 is the most preferable example, in which the tensile elastic modulus is 3896MPa, the flexural strength is 122.5MPa, and the flexural modulus is 3351MPa, and it can be seen that the silane coupling agent is most preferable in preparation example 17.
In summary, when the modified sol is prepared by mixing the resin, the modified filler and the surfactant according to the weight ratio of 1:0.25:0.04, and the silane coupling agent consists of vinyltriethoxysilane and methacryloxypropyltrimethoxysilane in a weight ratio of 1:1, the grafting or crosslinking effect of the modified glass fiber is optimal with the surface of the glass fiber and part of the hydroxylated glass fiber, so that the pre-modified glass fiber is endowed with excellent surface binding force, and the efficient implementation of subsequent modification treatment is ensured.
As can be seen by combining example 1, examples 24 to 26 and Table 3, examples 24 to 26 all had tensile elastic moduli higher than 3500MPa, flexural strengths higher than 121MPa and flexural moduli higher than 3000MPa.
Example 25 is the most preferred example having a tensile modulus of elasticity of 3610MPa, a flexural strength of 121.7MPa, and a flexural modulus of 3106MPa, and the surfactant of preparation example 13 is most preferred.
In summary, when the surfactant is prepared from diethylenetriamine, sodium dodecyl sulfate and glyceryl stearate according to the weight ratio of 1:1:1, the surface bonding performance of the pre-modified glass fiber can be obviously improved, and a bonding interface which is easy to crosslink between the surface of the pre-modified glass fiber and the mixed resin is formed between the surface of the pre-modified glass fiber and the mixed resin, so that the modification effect of the modified glass fiber is ensured.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (7)
1. The high-toughness plastic is characterized by comprising the following components in parts by weight:
87.4-91.4 parts of PBT;
0.3-0.5 part of lubricant;
0.3-0.5 part of antioxidant;
8-13 parts of modified glass fiber;
the preparation steps of the modified glass fiber are as follows:
a. pretreatment: preheating glass fiber to 80-100 ℃, then cooling to 0 ℃, and after vacuum drying, mixing the glass fiber with hydrogen peroxide according to the weight ratio of 1: (2-3) mixing, heating to 110-120 ℃, refluxing for 2-4h, and then adding a silane coupling agent, wherein the weight ratio of the silane coupling agent to the glass fiber is 1: (8-12), heating to 90-100 ℃, continuing to react for 3-6h, and after the reaction is finished, filtering and drying to obtain the silane modified glass fiber;
b. modification treatment: pre-modified glass fiber and modified sol are mixed according to the weight ratio of 1: (2-5) heating and reacting for 2-3h at 90-120 ℃ under vacuum condition to obtain modified glass fiber;
the modified sol is prepared from mixed resin, modified filler and surfactant according to a weight ratio of 1: (0.2-0.3): (0.03-0.05);
the mixed resin is prepared from carboxyl-terminated hyperbranched polyester, N-dimethylformamide and epoxy resin according to the weight ratio of 1: (0.8-1.2): (0.2-0.3).
2. The high-toughness plastic according to claim 1, wherein the modified filler is graphene, nano diatomite and nano silica in a weight ratio of 1: (0.2-0.3): (0.5-0.8).
3. The high toughness plastic of claim 1, wherein said surfactant is comprised of one or more of diethylenetriamine, sodium lauryl sulfate and glyceryl stearate.
4. A high-toughness plastic according to claim 1, wherein the silane coupling agent is one or more of vinyltriethoxysilane, methacryloxypropyltrimethoxysilane and aminosilanes.
5. A high-toughness plastic according to claim 1, wherein said lubricant consists of ethylene bisstearamide, zinc stearate and sorbitol in a weight ratio of 1: (0.5-0.8): (2-3).
6. A high-toughness plastic according to claim 1, wherein said antioxidant is prepared from thiobisphenol, benzophenone and p-phenylenediamine in a weight ratio of 1: (0.1-0.2): (0.8-1.2).
7. Process for the preparation of a high-toughness plastic as claimed in any one of claims 1 to 6, characterized in that it comprises the following steps:
s1, preparing materials: firstly, mixing the modified glass fiber, PBT, a lubricant and an antioxidant according to corresponding parts by weight to prepare mixed powder;
s2, pressing and sintering: adding the mixed powder into a mold, and heating and sintering after applying pressure, exhausting and maintaining pressure to prepare a sintered material;
s3, cooling: and cooling the sintered material to room temperature, and taking out the sintered material from the die to obtain the high-toughness plastic.
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| CN111518364A (en) * | 2020-06-15 | 2020-08-11 | 扬州爱非科鞋业有限公司 | Preparation method of high-temperature-resistant sole material |
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