CN110128034A - It nano-oxide fabricated in situ and is applied in polyester-type carbon fiber sizing agent and basalt fibre/glass fiber infiltration agent - Google Patents
It nano-oxide fabricated in situ and is applied in polyester-type carbon fiber sizing agent and basalt fibre/glass fiber infiltration agent Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/323—Polyesters, e.g. alkyd resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- 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
- D06M15/507—Polyesters
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- 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
- D06M2101/40—Fibres of carbon
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Abstract
The invention patent exploitation situ synthesis techniques prepare nano-oxide modified carbon fiber sizing agent, and basalt fibre/glass fiber infiltration agent, wherein nano-oxide includes silica, titanium dioxide, copper oxide, zinc oxide etc..Nano-oxide can be uniformly wrapped among polymer, the addition compared to traditional sizing agent nano silica significantly improves the heat-resistant stability of sizing agent.Content of the nano-oxide in sizing agent/size can be improved, and storage stability of the nano-oxide among sizing agent is improved using the method for self assembly self-emulsifying fabricated in situ.In addition the insertion of nano-oxide improves carbon fiber, basalt fibre/glass fibre surface energy, and the interface bond strength between fiber and resin can be improved.
Description
Technical field
The invention belongs to fiber interface modified additive fields, and in particular to a kind of anionic polyester that nano-oxide is modified
Type carbon fiber sizing agent, glass fibre/basalt fibre size.
Background technique
Fiber interface modified additive generally refers to carbon fiber sizing agent, glass fibre/basalt fibre size.Carbon fiber
Reinforced resin based composites are answered extensively because it is with light, high specific strength, high ratio modulus and good corrosion resistance
For fields such as military project, aerospace, automobile, Leisure Sports.Glass fibre/basalt fibre reinforcing composite material has because of it
Less expensive price also possesses wide market in certain specific occasions.Carbon fiber will pass through pre-oxidation in process of production,
A series of high temperature cabonization, processes such as graphitization, leads to the inert structure of carbon fiber surface, is unfavorable for and resin-bonded.Glass fibers
Dimension basalt fibre will cause fiber surface lousiness to be excessively difficult to add by techniques such as high-temperature fusion, wire drawings in process of production
Work.Therefore it needs in process of production to be surface-treated fiber.Carbon fiber sizing agent, glass fibre/basalt fibre leaching
Profit agent can play lubrication protection, cohere boundling, lint surface static charge buildup, and guarantee that it is preferably combined closely with resin
Effect.
Traditional carbon fibres sizing agent, glass fibre/basalt fibre fiber size, which generally uses, resin dispersion
It is prepared in solvent, but since organic solvent is volatile, safety problem is all brought to operator and factory.Just
Gradually replaced emulsion-type sizing agent.Emulsion-type sizing agent/size refers to is dispersed in water phase for resin in the form of an emulsion
In be prepared.Compared to solvent-borne type sizing agent/size, emulsion-type sizing agent/size has good starch finishing effect and work
Skill performance, it is nonflammable, in process of production the advantages that solvent-free volatilization.But emulsion-type sizing agent/size is being manufactured
A large amount of outer emulsifier to be added in the process, makes sizing agent/size heat resistance sharp fall.Therefore research and development have certainly
The carbon fiber sizing agent of emulsification function, glass fibre/basalt fibre size have very important research significance and industry
Value.
Carbon fiber sizing agent, glass fibre/basalt fibre size can be divided into asphalt mixtures modified by epoxy resin according to matrix resin difference
Epoxy-type, polyvinyl acetate type, polyester-type etc..According to similar compatibility principle, usually a kind of sizing agent/size can only match one kind
Resin, most of sizing agent/size that the current country uses are epoxide resin type, and expensive goods relies on import, uses epoxy
Resin type sizing agent/size treated fiber enhances in production composite material with other type of resin, Yi Shu
Interface unbound is generated at rouge and fiber interface, and many unfavorable factors are brought in terms of industrial production, seriously affect composite material
Mechanical property.Therefore research polyester-type sizing agent/size improves fiber and unsaturated-resin and vinylite composite wood
Expect interlaminar shear strength, has highly important value and significance for the development of fiber diversification resin compounded system chiasmate.
Using nano silica to carbon fiber sizing agent, glass fibre/basalt fibre size is modified is one
The relatively common method of modifying of kind, nano silica is amorphous white powder, and nontoxic, tasteless, pollution-free, micro-structure is
Spherical shape, molecular structure are in three-dimensional chain structure, so that bonding action, nanometer occur for nano silica and the certain functional groups of resin
Silica dioxide granule can enter inside resin matrix molecule segment, to greatly improve composite material toughness, intensity, ductility
Deng.The addition of nano silica can also generate effective ultraviolet radiation absorption simultaneously, and the optical characteristics such as infrared reflection and heat are steady
Qualitatively improve.
A kind of carbon fiber Wesy interface enhancement type nanometer silica disclosed in Chinese patent CN105297448B (grant number)
A certain proportion of nanometer silicon dioxide particle is added after epoxy resin and organic solvent diluting in modified epoxy sizing agent
It is sufficiently stirred, carries out vacuum distillation again after being uniformly dispersed and remove organic solvent, obtain nano-silicon dioxide modified epoxy
Resin.Suitable emulsifier is added in modified epoxy resin and distilled water carries out outer emulsification and obtains interface enhancement type nanometer two
Silica modified carbon fiber sizing agent, but carry out carbon fiber sizing agent obtained in this approach and generally require by organic solvent, wave
Great security risk is brought again while taking the energy, it is also necessary to by additional emulsifier, so that stability of emulsion and heat are steady
It is qualitative to be rung by inverted image.In addition, nano silica is directly added into, standing time length can make lotion generate precipitating aggregation.
The invention patent exploitation situ synthesis techniques prepare nano-oxide modified carbon fiber sizing agent, and basalt fibre/
Glass fiber infiltration agent, wherein nano-oxide includes silica, titanium dioxide, copper oxide, zinc oxide etc..It can be by nanometer
Oxide is uniformly wrapped among polymer, and the addition compared to traditional sizing agent nano silica significantly improves sizing agent
Heat-resistant stability.Content of the nano-oxide in sizing agent/size can be improved, and former using self assembly self-emulsifying
The method of position synthesis improves storage stability of the nano-oxide among sizing agent.In addition the insertion of nano-oxide mentions
High carbon fiber, basalt fibre/glass fibre surface can, the interface bond strength between fiber and resin can be improved.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of fabricated in situ nano-oxide modified carbon fiber sizing agent, glass
Glass fiber/basalt fibre size preparation method.Synthesis of polyhydroxy linear unsaturated polyester resin first, then to its into
The hydrophilic chain extension of row, introduces hydrophilic functional groups carboxyl, the oxide precursor of a certain amount of ratio, such as ethyl orthosilicate is added later
(TEOS), it is hydrolyzed in acid condition in butyl titanate, aluminium isopropoxide, zinc acetylacetonate, acetylacetone copper etc., to
Amine is added after being fully hydrolyzed and deionized water is neutralized, the modified polyester-type carbon fiber starching of nano-oxide can be obtained
Agent, glass fibre/basalt fibre size.Sizing agent/size preparation process of this method preparation is simple, using cream certainly
Change method avoids additional emulsifier, improves sizing agent/size thermal stability；Addition organic solvent is not needed, is kept away yet
The discharge of volatile organic compounds is exempted from；Using oxide precursor, such as ethyl orthosilicate (TEOS), butyl titanate, different
The method of the hydrolysis such as aluminium propoxide, zinc acetylacetonate, acetylacetone copper make TEOS etc. after hydrolysis generate silicone hydroxyl (Si-OH)/
Metal or nonmetallic-hydroxide (M-OH) key, are conducive to nano-oxide and organic polymer forms hybrid inorganic-organic, from
And improve dispersibility of the nano-oxide in lotion.The carbon fiber sizing agent produced using this method, the glass fibre/Black Warrior
Rock fiber size effectively reinforcing fiber and resin boundary surface interlaminar shear strength, raising nano-oxide can be modified sizing agent cream
The stability of liquid, while the addition of nano-oxide significantly improves sizing agent/size thermal stability.To solve above-mentioned skill
Art problem, the technical scheme is that
1. a kind of fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent, glass fibre/basalt
The preparation method of fiber size, it is characterised in that include the following steps:
(1) dicarboxylic acids/or acid anhydrides and unsaturated dicarboxylic acid/acid anhydrides and glycol monomer carry out polymerization reaction, synthesis
Carboxyl end group unsaturated polyester resin；
(2) epoxy resin is added and catalyst is reacted, epoxy group and the carboxyl end group of polyester is made to carry out open loop chain extension
Reaction；
(3) acid anhydrides is added and carries out esterification, generate chain extension, while generating hydrophilic carboxyl in polyester side chains；
(4) one or more of oxide precursors are added, as ethyl orthosilicate (TEOS), butyl titanate, aluminium isopropoxide,
Zinc acetylacetonate, acetylacetone copper etc. are fully hydrolyzed it in acid condition, are ultrasonically treated 5~20 minutes, form nano oxygen
Compound microballoon is uniformly distributed therein；
(5) be added salt forming agent in and carboxyl；
(6) deionized water stirring, which is added, can be obtained nano-oxide modified anion polyester-type carbon fiber sizing agent and profound
Military rock fiber/glass fiber infiltration agent.
2. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass
Fiber/basalt fibre size preparation method, which is characterized in that step (1) controls endpoint acid number in 30~40mg KOH/
Between g.
3. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass
Fiber/basalt fibre size preparation method, which is characterized in that in step (1), dicarboxylic acids or acid anhydrides are O-phthalic
Acid anhydrides, M-phthalic acid, terephthalic acid (TPA), methyl tetrahydro phthalic anhydride, hexahydro phthalic anhydride, hydrogenation M-phthalic acid, third
Diacid, succinic acid, adipic acid, dodecanedioic acid；Dihydric alcohol is ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,4- fourth two
Alcohol, 1,6- hexylene glycol, diethylene glycol (DEG), dipropylene glycol, Isosorbide-5-Nitrae-cyclohexanol, neopentyl glycol；Unsaturated dibasic acid or acid anhydrides are horse
Come acid anhydrides, fumaric acid anhydride, itaconic acid, tetrahydrophthalic anhydride；Reaction temperature is first reacted at 150 DEG C, prevents exothermic reaction and excessive alcohol
Then drain evaporation is warming up to 200-210 DEG C of progress esterification.
4. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass
Fiber/basalt fibre size preparation method, which is characterized in that epoxy resin is bisphenol type epoxy tree in step (2)
Rouge, bisphenol F epoxy resin, novolac epoxy resin, aliphatic linear epoxy resin, amine-modified epoxy resin etc., but be not limited to
These types；Reaction temperature is 100~120 DEG C, most preferably tends to 110~115 DEG C, the epoxide equivalent of epoxy resin be added is
100~1000.Selected catalyst be nitrogenous and phosphorus compound or metal salt or complex compound for example tertiary amine, quaternary ammonium salt, trialkyl phosphorus,
Quaternary alkylphosphonium salt, additional amount are the 0.01%~0.5% of total reactant weight.
5. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass
Fiber/basalt fibre size preparation method, which is characterized in that the acid anhydrides that step (3) is added is methyl tetrahydro phthalic anhydride, horse
Come acid anhydrides, succinic anhydride, phthalic anhydride, tetrabromophthalic anhydride or methyl hexahydrophthalic anhydride, hydroxyl value meter of the molal quantity of shared addition according to polyester
It calculates, circular are as follows: the molecular weight of acid anhydrides × (hydroxyl value of polyester × polyester quality)/(1000 × 56.1), reaction temperature
It is 100~150 DEG C, the reaction time is 1~3 hour.
6. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass
Fiber/basalt fibre size preparation method, which is characterized in that oxide precursor be added is positive silicon in step (4)
Acetoacetic ester (TEOS), butyl titanate, aluminium isopropoxide, zinc acetylacetonate, acetylacetone copper etc. are one such or several, ratio
Example is the 0~40% of polymer quality, and optimal proportion is 5%~20%.It is ultrasonically treated after it is fully hydrolyzed, makes its point
It dissipates uniform.
7. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass
The preparation method of fiber basalt fibre size, which is characterized in that the salt forming agent such as amine being added in step (5) is primary
Amine, secondary amine or tertiary amine, the salt forming agent molal quantity being added are equal to the molal quantity of acid anhydrides be added in step (4)；Temperature when addition
For room temperature~100 DEG C, the reaction time is 0.5~1 hour.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, and illustrative examples of the invention and explanation are used to
It explains the present invention, but is not intended as restriction of the invention.
Embodiment 1
24.05 grams of dipropylene glycol of the addition in 250 milliliters of reaction kettles, 23.89 grams of M-phthalic acid, neopentyl glycol
It 18.66 grams, gradually heats up under carbon dioxide atmosphere, in 200-210 DEG C of reaction until when acid value drops to 5 or less, is down to room
Temperature is added 16.63 grams of adipic acid, 11.16 grams of maleic acid, is continuously heating to 200-210 DEG C and is reacted, and controls acid value 40
Stop reaction afterwards.Protective gas changes nitrogen into and aromatic epoxy resin is added in when hypothermic response temperature in the kettle is to 100 DEG C or less
9.81 grams, 0.10 gram of catalyst, be slowly warming up to 110 DEG C the reaction was continued two hours, be then warming up to 115 DEG C of reactions again until
When acid value drops to 5 or less, 8.39 grams of methyl tetrahydro phthalic anhydride are added in 120 DEG C of two hours of reaction, cools down 50 DEG C and acetone is added
20 grams, be added 9 grams of TEOS, after its be stirring evenly and then adding into 3 grams of distilled water be fully hydrolyzed after be added 5.11 grams of triethylamine and
254 grams of progress salt-forming reactions of distilled water, 1817 grams of distilled water newborn acidifying and dilutions are added later can be obtained the nanometer of 5% solid content
Silica modified anionic polyester type carbon fiber sizing agent.
Domestic commercially available non-starching carbon fiber is taken to carry out starching processing by use for laboratory impregnation yarn device for sizing, it is slow to fiber
Slowly by slowly receiving silk after the abundant starching of steeping vat.The drying 1.5 hours of 120 DEG C of thermostatic drying chamber is put into after receiving silk.Take it is commercially available not
Saturated polyester resin (viscosity 800cps at 25 DEG C) carries out the production of interlaminar shear strength exemplar and test, cobalt accelerator proportion
It is the 0.1~0.2% of mass fraction.Curing agent proportion is the 1.5% of mass fraction, and it is 0.1% that mass fraction, which is added,
Acetylacetone,2,4-pentanedione.It is sufficiently applied to fiber surface after completely disappearing to resin bubble, fiber is laid among mold and carries out later
Deaeration touches tool and steps up fixed and elevated cure, and condition of cure is to solidify 8 hours at 60 DEG C.According to Chinese country, name republic
Standard GB/T 3096-2014 makes 2mm thickness, the batten of 6mm wide.The batten of production is cut into every piece of 30mm long, is made 10
Interlaminar shear strength test is carried out after a batten.
Embodiment 2
41.08 grams of neopentyl glycol of the addition in 250 milliliters of reaction kettles, 46.52 grams of adipic acid, 9.66 grams of maleic anhydride,
Gradually temperature reaction under carbon dioxide atmosphere, in 200-210 DEG C of reaction until acid value stops reaction after dropping to 35.Protective gas
Nitrogen and hypothermic response temperature in the kettle are changed into being added 9.53 grams of bisphenol A epoxide resin after 100 DEG C, 0.14 gram of catalyst, slowly
110 DEG C are warming up to the reaction was continued two hours, is then warming up to 115 DEG C of reactions again until first is added when acid value drops to 5 or less
7.7 grams of base tetrahydrophthalic anhydride, in 120 DEG C of two hours of reaction, cool down 50 DEG C and are added 20 grams of acetone, are added 10 grams of TEOS, stir to it
After mixing uniformly, 4.69 grams and 234 grams of distilled water of addition triethylamine after 3.4 grams of distilled water are fully hydrolyzed is added and carries out into salt,
2086 grams of water newborn acidifying and dilutions, which are added, can be obtained nano-silicon dioxide modified anionic polyester type carbon fiber sizing agent.
Method for sizing and test bars production method are identical as case 1.
Comparison example 1
Take carbon fiber (epoxy type) and same unsaturated polyester resin after the commercially available starching of same producer homogeneous in other conditions
Sample preparation and progress interlaminar shear strength test in the case where.
Comparison example 2
41.08 grams of neopentyl glycol of the addition in 250 milliliters of reaction kettles, 46.52 grams of adipic acid, 9.66 grams of maleic anhydride,
Gradually temperature reaction under carbon dioxide atmosphere, in 200-210 DEG C of reaction until acid value stops reaction after dropping to 35.Protective gas
Nitrogen and hypothermic response temperature in the kettle are changed into being added 9.53 grams of bisphenol A epoxide resin after 100 DEG C, 0.14 gram of catalyst, slowly
110 DEG C are warming up to the reaction was continued two hours, is then warming up to 115 DEG C of reactions again until first is added when acid value drops to 5 or less
7.7 grams of base tetrahydrophthalic anhydride, in 120 DEG C of two hours of reaction, are cooled to 4.69 grams of 60 degree of addition triethylamines and 234 distilled water carry out
1816 grams of distilled water are added later, is configured to 5% solid content sizing agent for emulsification.
Fiber starching and fibre reinforced composites batten manufacturing process are same as above breadboard example and comparison case is identical.
Test result shows that the interlaminar shear strength of embodiment 1 is 34.1MPa；The interlaminar shear strength of embodiment two is
30.1MPa；The interlaminar shear strength of comparative example 1 is 21.54 MPa；The interlaminar shear strength of comparative example 2 is
26.5MPa。
Test result shows the carbon fiber after Commercial epoxy resins type sizing agent starching and unsaturated polyester resin matching
Difference, it is obvious excellent using the interlaminar shear strength of carbon fiber and unsaturated polyester resin after homemade polyester-type sizing agent starching
In epoxide resin type sizing agent, furthermore the addition of inorganic nano silica can effectively improve the layer between carbon fiber and resin
Between shear strength.
Fig. 1 is carbon fiber surface SEM picture before and after carbon fiber starching, it can be seen that non-starching carbon fiber surface radial direction
There are many deep mixed grooves, stress is easy to cause to concentrate and crack when by load.Fabricated in situ Nano-meter SiO_22Forerunner
When body TEOS additional amount 5%, sizing agent emulsion is after carbon fiber surface starching, the available effective filling of surface gully, and
And it can be found that and adheres to some Nano-meter SiO_2s in carbon fiber surface2Particle is explained according to composite material mesh theory, is facilitated
Improve the interface bond strength between carbon fiber and resin.But when TEOS adding too much, Nano-meter SiO_2 can be generated2Part
Aggregation, causes carbon fiber doubling phenomena, influences resin when carbon fiber-reinforced resin in the permeability of carbon fiber surface, therefore to control
The additive amount for making TEOS is conducive to improve carbon fiber interface and the wellability of resin and its interlayer shear of composite material is strong
Degree.
Fig. 2 gives fabricated in situ Nano-meter SiO_22Carbon fibre surface energy before and after modified sizing agent emulsion starching tests knot
Fruit.Not silica containing test result is compared as can be seen from Figure 2, adds the amount of TEOS and present from 5%~10% gradually increasing
Trend, and the surface than being not added with TEOS can be high, at 10%, surface can reach and be up to 34.56mN/m, if continuing growing
The content of TEOS, carbon fibre surface energy are in downward trend again.Fiber surface can more big then fiber be easier and resin infiltration, right
Composite materials property improves then advantageously.
The different influences to stability of emulsion of 1 TEOS additive amount of table
Table 1 is analysis of the different TEOS additive amounts to sizing agent emulsion stability.Test result shows that TEOS additive amount exists
30 minutes and room temperature storage six months are centrifuged when 10% or less under 3000r/min revolving speed, sizing agent/infiltration agent emulsion does not all have
Precipitating generates, and illustrates that its storage stability is good, this is because using the nano-silicon dioxide modified sizing agent of fabricated in situ
Preparation method, nano silica are uniformly coated on wherein by polymer, improve its storage stability.
Claims (9)
1. a kind of fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent, glass fibre/basalt fibre
The preparation method of size, it is characterised in that include the following steps:
(1) dicarboxylic acids/or acid anhydrides and enter unsaturated dicarboxylic acid/acid anhydrides and glycol monomer carries out polymerization reaction, synthesize end
Carboxyl unsaturated polyester resin；
(2) epoxy resin is added and catalyst is reacted, epoxy group and the carboxyl end group of polyester is made to carry out open loop graft reaction；
(3) acid anhydrides is added and carries out carboxylation reaction, generate hydrophilic chain extension carboxyl；
(4) oxide precursor is added, such as TEOS, butyl titanate, zinc acetylacetonate, aluminium isopropoxide, acetylacetone copper, metatitanic acid
Four butyl esters, etc. it is therein any one or a few, be fully hydrolyzed it in acid condition, be ultrasonically treated 5 ~ 20 minutes, formed
Nano-oxide microballoon is uniformly distributed therein；
(5) be added salt forming agent in and carboxyl；
(6) deionized water stirring, which is added, can be obtained nano-oxide modified anion polyester-type carbon fiber sizing agent, glass fibers
Dimension/basalt fibre size.
2. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass fibre/
The preparation method of basalt fibre size, which is characterized in that step (1) control endpoint acid number 30 ~ 40mg KOH/g it
Between.
3. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass fibre/
The preparation method of basalt fibre size, which is characterized in that in step (1), dicarboxylic acids or acid anhydrides be phthalic anhydride,
M-phthalic acid, terephthalic acid (TPA), methyl tetrahydro phthalic anhydride, hexahydro phthalic anhydride, hydrogenation M-phthalic acid, malonic acid,
Succinic acid, adipic acid, dodecanedioic acid；Dihydric alcohol is ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,6-
Hexylene glycol, diethylene glycol (DEG), dipropylene glycol, Isosorbide-5-Nitrae-cyclohexanol, neopentyl glycol；Unsaturated dibasic acid or acid anhydrides be maleic anhydride,
Fumaric acid anhydride, itaconic acid, tetrahydrophthalic anhydride；Wherein mole of dihydric alcohol and dicarboxylic acids or acid anhydrides and unsaturated dibasic acid or acid anhydrides
Ratio is 2~1:1~2:, reaction temperature is first reacted at 150 DEG C, is prevented exothermic reaction and excessive alcohol drain evaporation, is then risen
Temperature arrives 200-210 DEG C of progress esterification.
4. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass fibre/
The preparation method of basalt fibre size, which is characterized in that epoxy resin is bisphenol A type epoxy resin, bis-phenol in step (2)
F epoxy resin, novolac epoxy resin, aliphatic linear epoxy resin, amine-modified epoxy resin etc. are one such or several
Combination, but it is not limited to these types；Reaction temperature is 100~120 DEG C, most preferably tends to 110~115 DEG C, epoxy resin be added
Epoxy resin equivalent be 100 ~ 1000.
5. catalyst selected by is nitrogenous and phosphorus compound or metal salt or complex compound such as tertiary amine, quaternary ammonium salt, trialkyl phosphorus, quaternary phosphine
Salt, additional amount are the 0.01% ~ 0.5% of total reactant weight.
6. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass fibre/
The preparation method of basalt fibre size, which is characterized in that the acid anhydrides that step (3) is added is methyl tetrahydro phthalic anhydride, maleic acid
The molal quantity of acid anhydride, succinic anhydride, phthalic anhydride, tetrabromophthalic anhydride or methyl hexahydrophthalic anhydride, shared addition is calculated according to the hydroxyl value of polyester, tool
Body calculation method are as follows: the molecular weight of acid anhydrides × (hydroxyl value of polyester × polyester quality)/(1000 × 56.1), reaction temperature 100
~ 150 DEG C, the reaction time is 1 ~ 3 hour.
7. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass fibre/
The preparation method of basalt fibre size, which is characterized in that TEOS be added, butyl titanate, acetylacetone,2,4-pentanedione in step (4)
The ratio of zinc, aluminium isopropoxide, acetylacetone copper, butyl titanate etc. be polymer quality 0 ~ 40%, optimal proportion be 5% ~
20%。
8. being ultrasonically treated after being fully hydrolyzed it, it is made to be uniformly dispersed.
9. fabricated in situ nano-oxide modified anion polyester-type carbon fiber sizing agent as described in claim 1, glass fibre/
The preparation method of basalt fibre size, which is characterized in that the salt forming agent such as amine being added in step (5) is primary amine, secondary
Amine or tertiary amine, the salt forming agent molal quantity being added are equal to the molal quantity of acid anhydrides be added in step (4)；Temperature is room temperature when addition
~100 DEG C, the reaction time is 0.5 ~ 1 hour.
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| CN113308899A (en) * | 2021-05-26 | 2021-08-27 | 东华大学 | Carbon fiber after surface sizing and preparation method and application thereof |
| CN114735949A (en) * | 2022-04-25 | 2022-07-12 | 江苏天龙玄武岩连续纤维股份有限公司 | Temperature-resistant fiber impregnating compound and preparation method thereof, and modified basalt fiber and preparation method thereof |
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