CN104592925A - Preparation method of flame-retardant carbon fibre impregnation adhesive and composite material thereof - Google Patents

Abstract

The invention discloses a flame-retardant carbon fibre impregnation adhesive for concrete structure reinforcing as well as a preparation method and a construction process of the flame-retardant carbon fibre impregnation adhesive. According to the invention, proper (single or combined) flame-retardant material ingredients are added in an epoxy resin curing system so that the flame-retardant carbon fibre impregnation adhesive meets the mandatory requirements of the national flame-retardant standards on flame-retardant building products and the mandatory requirements of the national standards related to building structure reinforcing on carbon fibre impregnation resin technical indexes; the flame-retardant carbon fibre impregnation adhesive is a normal-temperature cured double-component adhesive (adhesion resin) used for adhering a carbon fibre reinforcing composite material, is mainly composed of a modified epoxy resin system, a curing system, environment-friendly flame-retardant components and other auxiliaries, and achieves the effect of converting an impregnation resin which is inflammable with fire and generates lots of strong smoke to a flame-retardant and low-smoke impregnation resin; the adhesive and the adhesion process are suitable for reinforcing projects with fireproof requirements, such as public places, important structure reinforcing, wood structure reinforcing, strengthening and reinforcing for bridges, subway tunnels and air-raid shelters.

Description

A kind of flame retardant type impregnated carbon fiber tackiness agent and composite material and preparation method thereof thereof

Technical field

The present invention relates to a kind of binder composition, be specifically related to the carbon-fibre composite of a kind of flame retardant adhesive composition and use said composition thereof.

Background technology

Carbon fiber is a kind of Materials with High Strength, thus for having strict requirement to the wetting property of stickup resin, processing performance and physical and mechanical property during building structure reinforcement, the method of sticking carbon fiber reinforcing construction structure is the most common one of current field of reinforcement, by solvent impregnated resin, carbon fiber high for tensile strength is pasted the position of Structure of need reinforcement, make fiber and existing building structure jointly stressed, improve the intensity of structure, rigidity, splitting resistance and extensibility.Have saving space, easy construction, do not need on-the-spot fixation means, construction quality easily ensures, does not substantially increase scantlings of the structure and deadweight, the feature such as corrosion-resistant, excellent in durability.Binding resin should be epoxy resin organic polymer material, be easy to light, amount of heat is produced and dense smoke with intense stimulus produces during burning, fire can improve fire scene temperature when occurring, and then the enhancing intensity of a fire, expand the propagation of flame impetus and propagation rate, pungency dense smoke can hinder personnel escape and rescue personnel to sue and labour, causing larger loss of life and personal injury, is hiding some dangers for of fire when it is exposed when building structure is surperficial.

Summary of the invention

For solving the problem, the invention provides the carbon-fibre composite of a kind of flame retardant adhesive composition and use said composition thereof.Make solvent impregnated resin reach nonflammable material rank by technological prevention, stop the burning of carbon fiber composite layer, reduce the possibility causing fire to occur because of solvent impregnated resin, slow down spreading and propagating of the intensity of a fire, reduce pungency dense smoke.Meanwhile, construction technology performance and the physical and mechanical property of solvent impregnated resin is retained to greatest extent.

For achieving the above object, the technical scheme that the present invention takes is: a kind of flame retardant type impregnated carbon fiber tackiness agent, is prepared from by the two-pack of following weight part:

Component A:

B component:

Solidifying agent 25-50 part;

Silane coupling agent 0.1-2.0 part;

Curing catalyst 0.1-3.0 part.

For solving the problem, the embodiment of the present invention additionally provides the preparation method of above-mentioned a kind of flame retardant type impregnated carbon fiber tackiness agent, comprises the steps:

S1, take component respectively by formula according to claim 1;

S2, the solid that taken by step S1 are placed in after becoming mix with partially liq resin Composition and grind in grinding plant even, add the liquid ingredient that step S1 takes and mix in high-shear whipping device, the liquid dispersion of formation fire retardant adhesive;

S3, coat by bonding basal plane and carbon fibre fabric by the liquid dispersion of step S2 gained, roll-in is coated with and flatly forms flame retardant type carbon fiber composite layer after cured, and solidification value 20-40 DEG C, answers > 24h set time.

The present invention is by adding suitable fire retardant material (single or combination) composition in epoxy resin solidifying system, it is made to reach to meet concerned countries flame-retardant standard to reinforce the Compulsory Feature of standard for impregnated carbon fiber resin technology index for the Compulsory Feature of fire-retardant class building product and concerned countries, be applicable to the reinforcing engineering of fire protection requirement, as the reinforcing etc. of public place, important feature reinforcing, timber structure reinforcing, bridge, subway tunnel and civil air defense constructions and installations; This is a kind of professional two component adhesive (solvent impregnated resin) of the ambient cure for sticking carbon fiber strongthener, form primarily of modified epoxy resin system, curing system, environmental-protection flame-retardant component and other auxiliary agents, the effect that it reaches produces a large amount of dense smoke solvent impregnated resin when being and making inflammable chance fire changes into the difficult solvent impregnated resin firing low cigarette, fill up the blank of domestic flame retardant type carbon fibers adhere agent, cause construction unit, designing unit and supervisor to the attention of field of reinforcement having fire-retardant fireproof requirement.

Embodiment

In order to make objects and advantages of the present invention clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.

Each starting material choose that details are as follows:

1, epoxy resin

Adopt the various halogen epoxy resin that market is sold, mainly contain diglycidyl ether type epoxy resin and glycidyl ester epoxy resin.As bisphenol A type epoxy resin has: commodity are called E-51 (Japanese Dongdu chemical industry YD, oxirane value 0.51g/mol) etc.As bisphenol f type epoxy resin has: NPEF-170 (South Asia, Taiwan, oxirane value 0.60g/mol) etc.

2, epoxy resin toughener

Adopt polytype toughner that market is sold as base polyurethane prepolymer for use as, synthetic rubber, inorganic nano-particle etc.As terminal isocyanate group base polyurethane prepolymer for use as, epoxy-terminated polyurethane performed polymer (chemical industry garden, Shandong Zibo Shandong).As liquid acrylonitrile butadiene rubber, liquid nbr carboxyl terminal (Shanghai Lian Ying biochemical technology company limited).As nano-calcium carbonate (Ningbo Jiu Feng nanometer new forms of energy company limited).

3, nitrogenous organic fire-retardant

Adopt the poly-phosphate of nitrogenous organic base and the organic compounds containing nitrogen based on cyanuric acid that market is sold, the present invention selects the two mixture.As melamine pyrophosphate and cyanuric acid honey ammonium salt, trimeric cyanamide pentaphosphate and three (2-hydroxyethyl) chlorinated isocyanurates (Jinan Taixing Fine Chemicals Co., ltd).

4, phosphorous organic fire-retardant

Adopt the Organophosphorous compounds that market is sold, as ammonium polyphosphate, dimethyl methyl phosphonate, ethyl methylphosphonic acid diethyl ester, polyphenylene phosphoric acid (assorted-10-phosphono of 9,10-dihydro-9-oxy is assorted luxuriant and rich with fragrance) penylene ester (Yangzhou Chenhua Group Co., Ltd.).

5, inorganic combustion inhibitor

Adopt the inorganic combustion inhibitor that market is sold, as (Qingdao Lian Mei Chemical Co., Ltd.s) such as nano level superfine aluminium hydroxide, magnesium hydroxide, zinc borates.

6, solidifying agent

Prioritizing selection Polyamines Curing Agents of Epoxy Resins of the present invention, comprise aliphatic amide and modified fatty amine curing agent and aromatic amine and curing agent, as (Air Prod & Chem of the U.S.) such as diethylenetriamine, triethylene tetramine and affixture thereof, its amine of Manny, mphenylenediamine and derivatives thereof; Amide group amine; Polyetheramine etc.

The characteristic of embodiment 1-3 tackiness agent and carbon-fibre composite is by following methods:

(1) oxygen index

Oxygen index refers to that the material (test piece) of certain size loads in testing apparatus, under prescribed conditions, pass into the mixed gas of oxygen and nitrogen, test piece lighter for ignition is lighted, measure and keep minimum oxygen concn (representing with percentage ratio) as necessary in wax-like sustained combustion.

Examination criteria and detection method: GBT 2406.2-2009 plastics oxygen index method measures burning behavior

(2) smoke density

Smoke density refers to material the measuring of the amount of being fuming under prescribed test conditions, and it describes by the light intensity decays amount through cigarette. the material that smoke density is larger, and to evacuating personnel and fire extinguishing during fire more for unfavorable.

Examination criteria and detection method: the burning of GBT 8627-2007 material of construction or the smoke density test method of decomposing

(3) viscosifying power

Viscosifying power is that carbon fiber composite and base material (concrete, masonry and steel) just draw cohesive strength.

Examination criteria and detection method: GB 50728-2011 Reinforcement of Engineering Structure material safety authenticate technology specification

(4) carbon fiber composite tensile strength

Carbon fiber composite tensile strength is the expression that binder composition and carbon fibre material work in coordination with base material resistance to tension.

Examination criteria and detection method: GB 50728-2011 Reinforcement of Engineering Structure material safety authenticate technology specification

(5) monomer combustion experiment

Real fire scenario had both been considered in monomer combustion experiment, consider the end-use of material, was the gedanken experiment method of fibre composite combustionproperty in research real work.The experiment of application monomer combustion can obtain fibre composite dechforination in combustion: fire growth rate index (FIGRA), total heat release (THR), flue gas rate of rise (SMOGRA), total smoke-producing amount (TSP) etc.

Examination criteria and detection method: the monomer combustion test of GB 20284-2006 material of construction or goods

Embodiment 1:

Component A: halogen-free epoxy resin E-51 (trade names BE186, epoxy equivalent (weight) 180-190g/eq) 100 weight parts, terminal isocyanate group base polyurethane prepolymer for use as (-NCO content 4.8%) 10 weight parts, nitrogenous flame ratardant melamine cyanurate (trade names MCA, nitrogen content 48%) 10 weight parts, phosphonium flame retardant diethyl ethylphosphate (trade names DEEP, phosphorus content 18%) 10 weight parts, inorganic combustion inhibitor soft graphite (trade names ADT-20) 10 weight part.

B component: polyetheramine solidifying agent (trade names D-230) 30 weight part, modified fatty amine curing agent (trade names ANCAMD 2686) 20 weight parts, three-(dimethylamino methyl) phenol (trade names DMP-30) 2 weight parts, γ-aminopropyl triethoxysilane (trade names A-1100) 2 weight part.

Embodiment 2

Component A: halogen-free epoxy resin E-51 (trade names BE186, epoxy equivalent (weight) 180-190g/eq) 100 weight parts, liquid nbr carboxyl terminal (trade names CTBN) 15 weight part, nitrogenous flame ratardant melamine polyphosphate (trade names MPP, nitrogen content 18%) 15 weight parts, phosphonium flame retardant dimethyl methyl phosphonate (trade names DMMP, phosphorus content 25%) 15 weight parts, inorganic combustion inhibitor magnesium hydroxide (trade names HT-215, purity >=97.0) 10 weight parts.

B component: polyetheramine solidifying agent (trade names D-230) 20 weight part, modified fatty amine curing agent (trade names R-2017) 20 weight part, three-(dimethylamino methyl) phenol (trade names DMP-30) 2 weight parts, γ-aminopropyl triethoxysilane (trade names A-1100) 2 weight part.

Embodiment 3

Component A: halogen-free epoxy resin E-51 (trade names BE186, epoxy equivalent (weight) 180-190g/eq) 100 weight parts, nano-calcium carbonate (median size≤0.03 μm, purity >=99.0), nitrogenous flame ratardant melamine cyanurate (trade names MCA, nitrogen content 48%) 10 weight parts, phosphonium flame retardant ammonium polyphosphate (trade names APP, mean polymerisation degree >=1500), inorganic combustion inhibitor zinc borate (purity >=99.0) 10 weight part.

B component: different fluorine that ketone diamine curing agent (trade names IPDA) 20 weight part, modified fatty amine curing agent (trade names 5769) 20 weight parts, three-(dimethylamino methyl) phenol (trade names DMP-30) 2 weight parts, γ-aminopropyl triethoxysilane (trade names A-1100) 2 weight part.

Comparative example 1

Component A: halogen-free epoxy resin E-51 (trade names BE186, epoxy equivalent (weight) 180-190g/eq) 100 weight parts, terminal isocyanate group base polyurethane prepolymer for use as (-NCO content 4.8%) 10 weight parts.

B component: polyetheramine solidifying agent (trade names T-403) 20 weight part, modified fatty amine curing agent (trade names ANCAMD 2636) 10 weight parts, three-(dimethylamino methyl) phenol (trade names DMP-30) 2 weight parts, γ-aminopropyl triethoxysilane (trade names A-1100) 2 weight part.

Table 1 embodiment and comparative example composition burn performance and mechanics of fibre composites performance

Table 2 embodiment and comparative example monomer combustion experiments experiment result

From table 1,2, composition exhibiting prepared by embodiment 1 to embodiment 3 goes out good flame retardant properties, demonstrate good tensile strength, cohesive strength and flame retardant properties with carbon-fibre composite prepared by said composition, meet requirement of the present invention, there is important future in engineering applications.And comparative example 1 does not add fire-retardant component, composition with carbon-fibre composite compared with demand of the present invention time belong to inflammable material, apply limited.

In sum, this concrete enforcement is by adding suitable fire retardant material (single or combination) composition in epoxy resin solidifying system, it is made to reach to meet concerned countries flame-retardant standard to reinforce the Compulsory Feature of standard for impregnated carbon fiber resin technology index for the Compulsory Feature of fire-retardant class building product and concerned countries, be applicable to the CFRP reinforcing engineering of fire protection requirement, as the reinforcing etc. of public place, important feature reinforcing, timber structure reinforcing, bridge, subway tunnel and civil air defense constructions and installations; This is a kind of professional two component adhesive (solvent impregnated resin) of the ambient cure for sticking carbon fiber strongthener, form primarily of modified epoxy resin system, curing system, environmental-protection flame-retardant component and other auxiliary agents, the effect that it reaches produces a large amount of dense smoke solvent impregnated resin when being and making inflammable chance fire changes into the difficult solvent impregnated resin firing low cigarette, fill up the blank of domestic flame retardant type carbon fibers adhere agent, cause construction unit, designing unit and supervisor to the attention of field of reinforcement having fire-retardant fireproof requirement

The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (2)

1. a flame retardant type impregnated carbon fiber tackiness agent, is characterized in that, is prepared from by the two-pack of following weight part:

Component A:

B component:

2. the preparation method of a kind of flame retardant type impregnated carbon fiber tackiness agent as claimed in claim 1, is characterized in that, comprise the steps:

S1, take component respectively by formula according to claim 1;

S2, the solid that taken by step S1 are placed in after becoming mix with partially liq resin Composition and grind in grinding plant even, add the liquid ingredient that step S1 takes and mix in high-shear whipping device, the liquid dispersion of formation fire retardant adhesive;

S3, coat by bonding basal plane and carbon fibre fabric by the liquid dispersion of step S2 gained, roll-in is coated with and flatly forms flame retardant type carbon fiber composite layer after cured, and solidification value 20-40 DEG C, answers > 24h set time.