CN110079258A - A kind of high tenacity high temperature resistant shock resistance Load materials and preparation method - Google Patents

A kind of high tenacity high temperature resistant shock resistance Load materials and preparation method Download PDF

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Publication number
CN110079258A
CN110079258A CN201910288252.1A CN201910288252A CN110079258A CN 110079258 A CN110079258 A CN 110079258A CN 201910288252 A CN201910288252 A CN 201910288252A CN 110079258 A CN110079258 A CN 110079258A
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polyparaphenylene
parts
fiber
benzo dioxazole
temperature resistant
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CN110079258B (en
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王朝辉
韩冰
樊振通
陆由付
傅豪
迟朝明
陈宝
田垚
张长林
李林
周骊巍
曾伟
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Changan University
Shandong High Speed Group Co Ltd
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Qilu Transportation Development Group Co Ltd
Changan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2246—Esters of unsaturated carboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention provides a kind of high tenacity high temperature resistant shock resistance Load materials and preparation method thereof, method includes the following steps: step 1, it will be impregnated in ethylenediamine methanol solution by pretreated polyparaphenylene's benzo dioxazole fiber, and obtain ammonification polyparaphenylene benzo dioxazole fiber；Ammonification polyparaphenylene benzo dioxazole fiber obtained in step 1 and crylic acid ester mixture are carried out addition reaction, obtain acrylate-polyparaphenylene's benzo dioxazole fiber by step 2；Acrylate made from step 3-polyparaphenylene's benzo dioxazole fiber and hyperbranched polyorganosiloxane are carried out grafting processing by step 3, and modified polyparaphenylene's benzo dioxazole fiber is made；Modified polyparaphenylene's benzo dioxazole fiber made from step 3 is uniformly dispensed tiling, forms fiber by step 4, curing agent is added into epoxy resin prepares mould material, mould material is uniformly cast in the fiber skeleton of tiling, is solidified, high tenacity high temperature resistant shock resistance Load materials are made.

Description

A kind of high tenacity high temperature resistant shock resistance Load materials and preparation method
Technical field
The invention belongs to pavement material fields, are related to Load materials, and in particular to a kind of high tenacity high temperature resistant shock resistance road With material and preparation method.
Background technique
Asphalt roads interlaminar bonding influential effect Pavement Condition, interlaminar bonding deficiency will lead to bituminous pavement The diseases such as sliding, delamination and fatigue crack.And for bridge deck pavement, there is also same problems.As deck installation structure In the weakest system, the superiority and inferiority of waterproof-and-binding layer (i.e. bridge floor interlayer) is not only related to the use quality of deck paving, very To the structural life-time and military service performance for also affecting bridge entirety.Both at home and abroad in long-term research and application process, discovery Epoxy resin has apparent advantage in terms of deck paving interlayer bonding, and to consolidation discrete aggregate and improves waterproofness tool There is positive effect.But epoxy resin is mostly normal temperature cured type material, and solidification post-crosslinking density is high, solidfied material there are toughness it is low and The disadvantages of shock resistance is poor.In face of growing heavy traffic road demand, the flexibility and impact resistance of epoxy resin are not Foot affects the pavement performance of bridge deck pavement to a certain extent, thereby reduces road travel service level.Therefore it needs The toughness and intensity of reinforced epoxy make it have more excellent performance.
Summary of the invention
In view of the above shortcomings of the prior art with defect, the purpose of the present invention is to provide a kind of high tenacity high temperature resistant anti-impacts Load materials and preparation method are hit, the feature that toughness is low, high temperature resistance is poor after epoxy resin cure is solved.
In order to solve the above-mentioned technical problem, the present invention is realised by adopting the following technical scheme:
A kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, method includes the following steps:
Step 1 prepares ammonification polyparaphenylene benzo dioxazole fiber:
It will be impregnated in ethylenediamine methanol solution by pretreated polyparaphenylene's benzo dioxazole fiber, and obtain ammonification Polyparaphenylene's benzo dioxazole fiber；
Step 2 prepares acrylate-polyparaphenylene's benzo dioxazole fiber:
Ammonification polyparaphenylene benzo dioxazole fiber obtained in step 1 and crylic acid ester mixture are subjected to addition reaction, Obtain acrylate-polyparaphenylene's benzo dioxazole fiber；
Step 3 prepares modified polyparaphenylene's benzo dioxazole fiber:
Acrylate made from step 3-polyparaphenylene's benzo dioxazole fiber is grafted with hyperbranched polyorganosiloxane Modified polyparaphenylene's benzo dioxazole fiber is made in processing；
The molecular formula of the hyperbranched polyorganosiloxane are as follows:
Step 4 prepares high tenacity high temperature resistant shock resistance Load materials:
Modified polyparaphenylene's benzo dioxazole fiber made from step 3 is uniformly dispensed into tiling, fiber is formed, to epoxy Curing agent is added in resin and prepares mould material, mould material is uniformly cast in the fiber skeleton of tiling, is solidified, height is made Toughness high temperature resistant shock resistance Load materials.
The present invention also has following technical characteristic:
In step 1, the preprocessing process are as follows: remove polyparaphenylene's benzo dioxazole fiber in acetone soak 12h Surface attachments, taking-up are placed on 100 DEG C of dry 4h in air dry oven.By polyparaphenylene's benzo dioxazole fiber after drying It immerses in epoxychloropropane solution, and is irradiated with gamma-rays, then use acetone repeated flushing 12h, the dry 1h at 100 DEG C.
In step 1, pretreated polyparaphenylene's benzo dioxazole fiber will be passed through in the environment full of nitrogen, 12h is impregnated in 25 DEG C of ethylenediamine methanol solution, is then cleaned to pH=7, it is fine to obtain ammonification polyparaphenylene's benzo dioxazole Dimension.
In step 2, the detailed process of the addition reaction are as follows: by ammonification polyparaphenylene's benzo obtained in step 1 Dioxazole fiber and crylic acid ester mixture, and be added in methanol, then heating stirring for 24 hours, uses deionized water under 50 DEG C of environment Repeated flushing obtains acrylate-polyparaphenylene's benzo dioxazole fiber.
In step 3, the detailed process of the grafting processing are as follows: by acrylate-polyparaphenylene made from step 2 Benzo dioxazole fiber dry 0.5h at 100 DEG C, and transparent viscous liquid hyperbranched polyorganosiloxane is added, use methanol dilution Reaction mixture, and in 30 DEG C of heating 12h, it is then washed with deionized and dries 1.5h at 100 DEG C, be made modified poly- pair Penylene benzo dioxazole fiber.
In step 3, the preparation process of the hyperbranched polyorganosiloxane are as follows: by MPS, GPTMS, distilled water and anhydrous second Alcohol uniformly mixes in proportion, and adjusting solution ph is 5.0~6.0, is then heated to 60 DEG C, reacts 4h, and obtained product is true Sky is dry and except what is generated in dereaction mixes solvent, obtains hyperbranched polyorganosiloxane.
Specifically, based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 8~16 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 25~45 parts of polyparaphenylene's benzo dioxazole fiber Raw material is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 8~20 parts, and GPTMS is 8~25 parts, and distilled water is 16~30 parts, and dehydrated alcohol is 40~55 parts.
It is furthermore preferred that based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 12~16 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 25~30 parts of polyparaphenylene's benzo dioxazole fiber Raw material is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 8~10 parts, and GPTMS is 8~12 parts, and distilled water is 16~20 parts, and dehydrated alcohol is 40~50 parts.
Most preferably, based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 25 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 8 parts, and GPTMS is 8 parts, and distilled water is 6 parts, and dehydrated alcohol is 40 parts.
In step 4, the solidification temperature is 80 DEG C.
A kind of high tenacity high temperature resistant shock resistance Load materials, the material use high tenacity high temperature resistant shock resistance as described above The preparation method of Load materials is made.
Compared with prior art, the present invention having the following technical effect that
(I) hyperbranched polyorganosiloxane and the processing of polyparaphenylene's benzo dioxazole fibre grafting are applied to road for the first time by the present invention Road asphalt modification fiber art.Hyperbranched polyorganosiloxane have hyperbranched structure and superior performance, synthesis mode multiplicity and Simply, process control.
(II) polyparaphenylene's benzo dioxazole fiber that the present invention uses is with 4,6-diaminoresorcinol and trimethyl Silazane is raw material using one kind made from trimethylsilyl method containing heteroaromatic polyamide, and heat resisting temperature is up to 600 DEG C, there are the excellent properties such as high intensity, high thermal stability, corrosion-resistant, oxidative resistance and moisture resistance, polyphosphoric acids can be dissolved in With polyphosphoric acids methane sulfonic acid equal solvent, there is positive effect to epoxy resin impact resistance and heat-resisting quantity is improved.
(III) hyperbranched polyorganosiloxane is using Si-O as main chain, and-OH is the highly branched polymer of side group, is had both organic The excellent performances such as high fluidity, corrosion resistance, weatherability, the low-viscosity of the high-fire resistance of silicon polymer and dissaving polymer, The modifying agent that can be used as epoxy resin improves the impact resistance and toughness of epoxy resin while guaranteeing stability.
(IV) hyperbranched polyorganosiloxane molecule prepared by the present invention carries active function groups, and molecular end contains a large amount of branch The groups such as chain and silicon chlorine, silicon hydrogen are easy to functional modification, can be used for fiber surface grafting processing, significantly improve polyparaphenylene's benzo The activity of dioxazole fiber, the roughness on reinforcing fiber surface improve the bond effect of fiber and epoxy resin.
(V) it is low, anti-to can effectively improve epoxy resin toughness for modified polyparaphenylene's benzo dioxazole fiber prepared by the present invention The disadvantages of poor, high temperature resistant is poor is impacted, can be widely applied for various bridge deck pavements.
Explanation is further explained in detail to particular content of the invention with reference to embodiments.
Specific embodiment
It should be noted that MPS is γ-methacryloxypropyl trimethoxy in following embodiment and comparative examples Silane；GPTMS is γ-glycidyl ether oxygen propyl trimethoxy silicane.
The molecular formula of hyperbranched polyorganosiloxane are as follows:
Curing agent is phthalic anhydride.
Epoxy resin is E-42 epoxy resin.
The structural formula of polyparaphenylene's benzo dioxazole fiber are as follows:
Wherein: n=50~120.
The preparation process of polyparaphenylene's benzo dioxazole fiber are as follows: with 4,6-diaminoresorcinol and trimethyl silicane azane For raw material, it is made using trimethylsilyl method.
The heat resisting temperature of polyparaphenylene's benzo dioxazole fiber has excellent thermal stability, can be dissolved in more up to 600 DEG C Polyphosphoric acid and polyphosphoric acids methane sulfonic acid equal solvent.
Specific embodiments of the present invention are given below, it should be noted that the invention is not limited to implement in detail below Example, all equivalent transformations made on the basis of the technical solutions of the present application each fall within protection scope of the present invention.
Embodiment 1:
The present embodiment provides a kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, and this method includes following step It is rapid:
Step 1 prepares ammonification polyparaphenylene benzo dioxazole fiber:
It will be impregnated in ethylenediamine methanol solution by pretreated polyparaphenylene's benzo dioxazole fiber, and obtain ammonification Polyparaphenylene's benzo dioxazole fiber；
In step 1, preprocessing process are as follows: polyparaphenylene's benzo dioxazole fiber is attached on acetone soak 12h removal surface Object, taking-up be placed on 100 DEG C of dry 4h in air dry oven.Polyparaphenylene's benzo dioxazole fiber after drying is immersed into ring It in oxygen chloropropane solution, and is irradiated with gamma-rays, then uses acetone repeated flushing 12h, the dry 1h at 100 DEG C.
In step 1, pretreated polyparaphenylene's benzo dioxazole fiber will be passed through in the environment full of nitrogen, 12h is impregnated in 25 DEG C of ethylenediamine methanol solution, is then cleaned to pH=7, it is fine to obtain ammonification polyparaphenylene's benzo dioxazole Dimension.
Step 2 prepares acrylate-polyparaphenylene's benzo dioxazole fiber:
Ammonification polyparaphenylene benzo dioxazole fiber obtained in step 1 and crylic acid ester mixture are subjected to addition reaction, Obtain acrylate-polyparaphenylene's benzo dioxazole fiber；
In step 2, the detailed process of addition reaction are as follows: by ammonification polyparaphenylene benzo dioxazole obtained in step 1 Fiber and crylic acid ester mixture, and be added in methanol, then heating stirring for 24 hours, is rushed repeatedly with deionized water under 50 DEG C of environment It washes to obtain acrylate-polyparaphenylene's benzo dioxazole fiber.
Step 3 prepares modified polyparaphenylene's benzo dioxazole fiber:
Acrylate made from step 3-polyparaphenylene's benzo dioxazole fiber is grafted with hyperbranched polyorganosiloxane Modified polyparaphenylene's benzo dioxazole fiber is made in processing；
In step 3, the detailed process of grafting processing are as follows: by acrylate made from step 2-polyparaphenylene's benzo two Oxazole fiber dry 0.5h at 100 DEG C, and transparent viscous liquid hyperbranched polyorganosiloxane is added, react mixed with methanol dilution Object is closed, and in 30 DEG C of heating 12h, be then washed with deionized and dry 1.5h at 100 DEG C, modified polyparaphenylene's benzene is made And dioxazole fiber.
In step 3, the preparation process of hyperbranched polyorganosiloxane are as follows: by MPS, GPTMS, distilled water and dehydrated alcohol press than Example uniformly mixing, adjusting solution ph is 5.0~6.0, is then heated to 60 DEG C, reacts 4h, and obtained product vacuum is dry And except what is generated in dereaction mixes solvent, hyperbranched polyorganosiloxane is obtained.
Step 4 prepares high tenacity high temperature resistant shock resistance Load materials:
Modified polyparaphenylene's benzo dioxazole fiber made from step 3 is uniformly dispensed into tiling, fiber is formed, to epoxy Curing agent is added in resin and prepares mould material, mould material is uniformly cast in the fiber skeleton of tiling, is solidified, height is made Toughness high temperature resistant shock resistance Load materials.
In step 4, solidification temperature is 80 DEG C.
In the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment, the proportion of each primary raw material, with Parts by weight meter:
Every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 25 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 8 parts, and GPTMS is 8 parts, and distilled water is 6 parts, and dehydrated alcohol is 40 parts.
It is anti-that high tenacity high temperature resistant is made using the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment Impact Load materials.
Embodiment 2:
The present embodiment provides a kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, the preparation step of this method Substantially the same manner as Example 1, difference is, in the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment, The proportion of each primary raw material, based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 10 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 30 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 8 parts, and GPTMS is 10 parts, and distilled water is 16 parts, and dehydrated alcohol is 40 parts.
It is anti-that high tenacity high temperature resistant is made using the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment Impact Load materials.
Embodiment 3:
The present embodiment provides a kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, the preparation step of this method Substantially the same manner as Example 1, difference is, in the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment, The proportion of each primary raw material, based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 25 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 8 parts, and GPTMS is 8 parts, and distilled water is 16 parts, and dehydrated alcohol is 40 parts.
It is anti-that high tenacity high temperature resistant is made using the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment Impact Load materials.
Embodiment 4:
The present embodiment provides a kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, the preparation step of this method Substantially the same manner as Example 1, difference is, in the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment, The proportion of each primary raw material, based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 25 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 10 parts, and GPTMS is 12 parts, and distilled water is 20 parts, and dehydrated alcohol is 50 parts.
It is anti-that high tenacity high temperature resistant is made using the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment Impact Load materials.
Embodiment 5:
The present embodiment provides a kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, the preparation step of this method Substantially the same manner as Example 1, difference is, in the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment, The proportion of each primary raw material, based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 16 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 30 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 10 parts, and GPTMS is 12 parts, and distilled water is 20 parts, and dehydrated alcohol is 50 parts.
It is anti-that high tenacity high temperature resistant is made using the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment Impact Load materials.
Embodiment 6:
The present embodiment provides a kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, the preparation step of this method Substantially the same manner as Example 1, difference is, in the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment, The proportion of each primary raw material, based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 16 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 30 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 15 parts, and GPTMS is 16 parts, and distilled water is 25 parts, and dehydrated alcohol is 50 parts.
It is anti-that high tenacity high temperature resistant is made using the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment Impact Load materials.
Embodiment 7:
The present embodiment provides a kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, the preparation step of this method Substantially the same manner as Example 1, difference is, in the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment, The proportion of each primary raw material, based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 10 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 40 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 15 parts, and GPTMS is 20 parts, and distilled water is 25 parts, and dehydrated alcohol is 50 parts.
It is anti-that high tenacity high temperature resistant is made using the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment Impact Load materials.
Embodiment 8:
The present embodiment provides a kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, the preparation step of this method Substantially the same manner as Example 1, difference is, in the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment, The proportion of each primary raw material, based on parts by weight:
Every 100 parts of epoxy resin is corresponding to be added 8 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 45 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 20 parts, and GPTMS is 25 parts, and distilled water is 30 parts, and dehydrated alcohol is 55 parts.
It is anti-that high tenacity high temperature resistant is made using the preparation method of the high tenacity high temperature resistant shock resistance Load materials of the present embodiment Impact Load materials.
Comparative example 1:
This comparative example provides a kind of preparation method of Load materials, method includes the following steps:
Curing agent is added into epoxy resin and prepares mould material, and mould material is directly solidified at 80 DEG C, road is made Use material.
Same as Example 1, every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent.
The raw material used in this comparative example is same as Example 1.
Comparative example 2:
This comparative example provides a kind of preparation method of Load materials, method includes the following steps:
Polyparaphenylene's benzo dioxazole fiber is uniformly dispensed into tiling, fiber is formed, curing agent is added into epoxy resin Mould material is prepared, mould material is uniformly cast in the fiber skeleton of tiling, is solidified at 80 DEG C, Load materials are made.
Same as Example 1, every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent；
Polyparaphenylene's benzo dioxazole fiber that the corresponding fiber skeleton being added of every 100 parts of epoxy resin is 25 parts.
The raw material used in this comparative example is same as Example 1.
Comparative example 3:
This comparative example provides a kind of preparation method of Load materials, method includes the following steps:
Curing agent is added into epoxy resin and hyperbranched polyorganosiloxane prepares mould material, and mould material is uniformly poured In the fiber skeleton of tiling, solidify at 80 DEG C, Load materials are made.
Same as Example 1, every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 8 parts, and GPTMS is 8 parts, and distilled water is 6 parts, and dehydrated alcohol is 40 parts.
The raw material used in this comparative example is same as Example 1.
Comparative example 4:
This comparative example provides a kind of preparation method of Load materials, method includes the following steps:
Step 1 prepares ammonification polyparaphenylene benzo dioxazole fiber:
Ammonia is prepared in the step of process of this comparative example preparation ammonification polyparaphenylene benzo dioxazole fiber and embodiment 1 one The method for changing polyparaphenylene's benzo dioxazole fiber is identical.
Step 2 prepares Load materials:
Ammonification polyparaphenylene benzo dioxazole fiber made from step 1 is uniformly dispensed into tiling, forms fiber skeleton, to Curing agent is added in epoxy resin and prepares mould material, mould material is uniformly cast in the fiber skeleton of tiling, at 80 DEG C Load materials are made in lower solidification.
Same as Example 1, every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is polyparaphenylene's benzo dioxazole fiber system using 25 parts At ammonification polyparaphenylene's benzo dioxazole fiber.
The raw material used in this comparative example is same as Example 1.
Comparative example 5:
This comparative example provides a kind of preparation method of Load materials, method includes the following steps:
Step 1 prepares ammonification polyparaphenylene benzo dioxazole fiber:
Ammonia is prepared in the step of process of this comparative example preparation ammonification polyparaphenylene benzo dioxazole fiber and embodiment 1 one The method for changing polyparaphenylene's benzo dioxazole fiber is identical.
Step 2 prepares acrylate-polyparaphenylene's benzo dioxazole fiber:
This comparative example was prepared in the step of acrylate-polyparaphenylene's benzo dioxazole fiber process and embodiment 1 two It is identical to prepare acrylate-polyparaphenylene's benzo dioxazole fiber method.
Step 3 prepares Load materials:
Acrylate made from step 2-polyparaphenylene's benzo dioxazole fiber is uniformly dispensed into tiling, forms fiber bone Frame adds curing agent into epoxy resin and prepares mould material, mould material is uniformly cast in the fiber skeleton of tiling, Solidify at 80 DEG C, Load materials are made.
Same as Example 1, every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is polyparaphenylene's benzo dioxazole fiber system using 25 parts At acrylate-polyparaphenylene's benzo dioxazole fiber.
The raw material used in this comparative example is same as Example 1.
Comparative example 6:
This comparative example provides a kind of preparation method of Load materials, method includes the following steps:
Step 1 prepares ammonification polyparaphenylene benzo dioxazole fiber:
Ammonia is prepared in the step of process of this comparative example preparation ammonification polyparaphenylene benzo dioxazole fiber and embodiment 1 one The method for changing polyparaphenylene's benzo dioxazole fiber is identical.
Step 2 prepares modified polyparaphenylene's benzo dioxazole fiber:
The modification prepared in the step of modification polyparaphenylene benzo dioxazole fiber of this comparative example preparation and embodiment 1 three Polyparaphenylene's benzo dioxazole fiber is different, the difference is that directly disliking to the ammonification polyparaphenylene benzo two of step 1 preparation Azoles fiber is modified, without using acrylate.It is specific as follows:
Ammonification polyparaphenylene benzo dioxazole fiber made from step 1 is modified fiber and hyperbranched polyorganosiloxane Grafting processing is carried out, modified polyparaphenylene's benzo dioxazole fiber is made；
In step 2, the detailed process of grafting processing are as follows: by ammonification polyparaphenylene benzo dioxazole made from step 1 Fiber dry 0.5h at 100 DEG C, and transparent viscous liquid hyperbranched polyorganosiloxane is added, it is reacted and is mixed with methanol dilution Object, and in 30 DEG C of heating 12h, it is then washed with deionized and dries 1.5h at 100 DEG C, modified polyparaphenylene's benzo is made Dioxazole fiber.
Hyperbranched polyorganosiloxane in step 2, in the preparation process of hyperbranched polyorganosiloxane and the step of embodiment 1 three Preparation process it is identical.
Step 3 prepares Load materials:
Modified polyparaphenylene's benzo dioxazole fiber made from step 2 is uniformly dispensed into tiling, forms fiber skeleton, to Curing agent is added in epoxy resin and prepares mould material, mould material is uniformly cast in the fiber skeleton of tiling, at 80 DEG C Load materials are made in lower solidification.
Same as Example 1, every 100 parts of epoxy resin is corresponding to be added 12 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is polyparaphenylene's benzo dioxazole fiber system using 25 parts At modification polyparaphenylene's benzo dioxazole fiber.
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials； MPS is 8 parts, and GPTMS is 8 parts, and distilled water is 6 parts, and dehydrated alcohol is 40 parts.
The raw material used in this comparative example is same as Example 1.
Performance test:
For tensile strength, elongation at break, low temperature flexibility and the anti-shearing, anti-pulling and shock resistance for verifying Load materials Intensity, according to " Test methods for building waterproof coatings " (GB/T 16777-2008) and " resin-cast body method for testing performance " The relevant regulations of (GB/T 2567-2008) etc. carry out basic nature to Load materials obtained in the embodiment of the present invention and comparative example Energy test and simulation laboratory test, the results are shown in Table 1.
The performance test results of Load materials obtained in 1 embodiment and comparative example of table
Known to analytical table 1:
(1) comparative example 1~6 is analyzed it is found that hyperbranched polyorganosiloxane is with poly- to benzene compared with untreated epoxy resin Support benzo dioxazole fiber can significantly improve the toughness and intensity of epoxy resin；At through polyparaphenylene's benzo dioxazole fiber The epoxy resin of reason is compared, and hyperbranched polyorganosiloxane can more improve the tensile strength of epoxy resin.
(2) Examples 1 to 7 and comparative example 1~6 are analyzed it is found that compared with untreated epoxy resin prepared by the present invention Load materials tensile strength, break-draw rate, impact strength significantly improve, illustrate the toughness of material, adhesive property and strong Degree is improved；Do not crack under the conditions of -20 DEG C, 90 °, illustrate that material at low temperature toughness enhances, under the conditions of high temperature (70 DEG C) with Shearing strength is compared decline with adhesion strength and is not obvious under the conditions of room temperature (25 DEG C), illustrates that material has preferable heat-resisting quantity Energy.
(3) Examples 1 to 8 and comparative example 2 are analyzed it is found that with the asphalt mixtures modified by epoxy resin through polyparaphenylene's benzo dioxazole fiber treatment Lipid phase has better performance than Load materials of the invention, this is because hyperbranched polyorganosiloxane molecular surface has a large amount of functions Group can react with polyparaphenylene's benzo dioxazole fiber, improve fiber-reactive, can significantly improve polyparaphenylene's benzo The bond effect of dioxazole fiber and epoxy resin.
(4) analysis comparative example 2,4,6 is it is found that prepare Load materials with hyperbranched polyorganosiloxane is directly grafted after fiber ammonification It compares, there is better bond effect through acrylate treated ammonification polyparaphenylene benzo dioxazole fiber and epoxy resin And flexibility, this is because acrylate has a good adhesive strength, and stick portion has certain impact resistance and tough Property.
(5) it analyzes Examples 1 to 8 and finds that 1 indices performance of embodiment is best it is found that can integrate, best raw material Composition are as follows: 8 parts of γ-methacryloxypropyl trimethoxy silane (MPS), γ-glycidyl ether oxygen propyl trimethoxy 8 parts of silane (GPTMS), 16 parts of distilled water, 40 parts of dehydrated alcohol, 25 parts of polyparaphenylene's benzo dioxazole fiber, epoxy resin 100 Part, 12 parts of curing agent.

Claims (10)

1. a kind of preparation method of high tenacity high temperature resistant shock resistance Load materials, which is characterized in that method includes the following steps:
Step 1 prepares ammonification polyparaphenylene benzo dioxazole fiber:
It will be impregnated in ethylenediamine methanol solution by pretreated polyparaphenylene's benzo dioxazole fiber, and obtain poly- pair of ammonification Penylene benzo dioxazole fiber；
Step 2 prepares acrylate-polyparaphenylene's benzo dioxazole fiber:
Ammonification polyparaphenylene benzo dioxazole fiber obtained in step 1 and crylic acid ester mixture are subjected to addition reaction, obtained Acrylate-polyparaphenylene's benzo dioxazole fiber；
Step 3 prepares modified polyparaphenylene's benzo dioxazole fiber:
Acrylate made from step 3-polyparaphenylene's benzo dioxazole fiber and hyperbranched polyorganosiloxane are carried out at grafting Modified polyparaphenylene's benzo dioxazole fiber is made in reason；
The molecular formula of the hyperbranched polyorganosiloxane are as follows:
Step 4 prepares high tenacity high temperature resistant shock resistance Load materials:
Modified polyparaphenylene's benzo dioxazole fiber made from step 3 is uniformly dispensed into tiling, fiber is formed, to epoxy resin Middle addition curing agent prepares mould material, mould material is uniformly cast in the fiber skeleton of tiling, and high tenacity is made in solidification High temperature resistant shock resistance Load materials.
2. the preparation method of high tenacity high temperature resistant shock resistance Load materials as described in claim 1, which is characterized in that step 1 In, the preprocessing process are as follows: polyparaphenylene's benzo dioxazole fiber is removed into surface attachments in acetone soak 12h, is taken It is placed on 100 DEG C of dry 4h in air dry oven out；Polyparaphenylene's benzo dioxazole fiber after drying is immersed into epoxy chloropropionate It in alkane solution, and is irradiated with gamma-rays, then uses acetone repeated flushing 12h, the dry 1h at 100 DEG C.
3. the preparation method of high tenacity high temperature resistant shock resistance Load materials as described in claim 1, which is characterized in that step 1 In, pretreated polyparaphenylene's benzo dioxazole fiber will be passed through in the environment full of nitrogen, in 25 DEG C of ethylenediamine first Then alcohol solution for soaking 12h is cleaned to pH=7, to obtain ammonification polyparaphenylene's benzo dioxazole fiber.
4. the preparation method of high tenacity high temperature resistant shock resistance Load materials as described in claim 1, which is characterized in that step 2 In, the detailed process of the addition reaction are as follows: by ammonification polyparaphenylene benzo dioxazole fiber obtained in step 1 and third The mixing of olefin(e) acid ester, and be added in methanol, then heating stirring for 24 hours, obtains third with deionized water repeated flushing under 50 DEG C of environment Olefin(e) acid ester-polyparaphenylene's benzo dioxazole fiber.
5. the preparation method of high tenacity high temperature resistant shock resistance Load materials as described in claim 1, which is characterized in that step 3 In, the detailed process of the grafting processing are as follows: by acrylate made from step 2-polyparaphenylene's benzo dioxazole fiber The dry 0.5h at 100 DEG C, and transparent viscous liquid hyperbranched polyorganosiloxane is added, with methanol dilution reaction mixture, and In 30 DEG C of heating 12h, then it is washed with deionized and the dry 1.5h at 100 DEG C, obtained modified polyparaphenylene's benzo two is disliked Azoles fiber.
6. the preparation method of high tenacity high temperature resistant shock resistance Load materials as described in claim 1, which is characterized in that step 3 In, the preparation process of the hyperbranched polyorganosiloxane are as follows: uniformly mix MPS, GPTMS, distilled water and dehydrated alcohol in proportion It closes, adjusting solution ph is 5.0~6.0, is then heated to 60 DEG C, reacts 4h, by the drying of obtained product vacuum and is removed anti- That answers middle generation mixes solvent, obtains hyperbranched polyorganosiloxane.
7. the preparation method of high tenacity high temperature resistant shock resistance Load materials as claimed in claim 6, which is characterized in that with weight Number meter:
Every 100 parts of epoxy resin is corresponding to be added 8~16 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 25~45 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials；MPS is 8~20 parts, GPTMS is 8~25 parts, and distilled water is 16~30 parts, and dehydrated alcohol is 40~55 parts.
8. the preparation method of high tenacity high temperature resistant shock resistance Load materials as claimed in claim 6, which is characterized in that with weight Number meter:
Every 100 parts of epoxy resin is corresponding to be added 12~16 parts of curing agent；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin uses 25~30 parts of polyparaphenylene's benzo dioxazole fibrous raw material It is made；
The corresponding fiber skeleton being added of every 100 parts of epoxy resin is using the hyperbranched polyorganosiloxane being prepared from the following raw materials；MPS is 8~10 parts, GPTMS is 8~12 parts, and distilled water is 16~20 parts, and dehydrated alcohol is 40~50 parts.
9. the preparation method of high tenacity high temperature resistant shock resistance Load materials as described in claim 1, which is characterized in that described Curing agent is phthalic anhydride；The epoxy resin is E-42 epoxy resin；
The structural formula of polyparaphenylene's benzo dioxazole fiber are as follows:
Wherein: n=50~120.
10. a kind of high tenacity high temperature resistant shock resistance Load materials, which is characterized in that the material is used as claim 1 to 9 is any The preparation method of high tenacity high temperature resistant shock resistance Load materials described in claim is made.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101319084A (en) * 2008-07-17 2008-12-10 上海交通大学 Preparation method for poly-p-phenylene-benzo-dioxazole fibre/epoxy resin composite material
CN109265922A (en) * 2018-08-17 2019-01-25 西北工业大学 A kind of high tenacity self-catalysis epoxy resin and preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101319084A (en) * 2008-07-17 2008-12-10 上海交通大学 Preparation method for poly-p-phenylene-benzo-dioxazole fibre/epoxy resin composite material
CN109265922A (en) * 2018-08-17 2019-01-25 西北工业大学 A kind of high tenacity self-catalysis epoxy resin and preparation method

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