CN108484891A - The preparation of self assembly self-emulsifying self-stabilization polyester-type high-performance fiber interface modification auxiliary agent and product and application - Google Patents
The preparation of self assembly self-emulsifying self-stabilization polyester-type high-performance fiber interface modification auxiliary agent and product and application Download PDFInfo
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- CN108484891A CN108484891A CN201810198746.6A CN201810198746A CN108484891A CN 108484891 A CN108484891 A CN 108484891A CN 201810198746 A CN201810198746 A CN 201810198746A CN 108484891 A CN108484891 A CN 108484891A
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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
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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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
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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Abstract
The present invention provides preparation and product and the application of a kind of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive.Dicarboxylic acids/or acid anhydrides and glycol monomer carry out polymerisation, and unsaturated dibasic acid/acid anhydrides is added after cooling, and the reaction was continued, and the dicarboxylic acids/or acid anhydrides for high reaction activity merge above-mentioned reaction；Epoxy resin is added and catalyst is reacted, the end carboxyl of epoxy group and polyester is made to carry out open loop graft reaction, acid anhydrides is added and carries out carboxylation reaction, generates hydrophilic chain extension carboxyl；Later be added salt forming agent in and carboxyl, be eventually adding deionized water and can be obtained with self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive.The fiber interface modified additive prepared using the present invention can effectively solve the problems such as collection of filaments is bad and bad with resin compatible with fiber fiber separation, and stability of emulsion is resolved, and half a year is stored under room temperature, and there is no precipitate.
Description
Technical field
The present invention relates to a kind of preparation of fiber interface modified additive and product and applications, more particularly to a kind of self assembly
The preparation of self-emulsifying self-stabilization polyester-type high-performance fiber interface modification auxiliary agent and product and application.
Background technology
High-performance fiber refers to carbon fiber, basalt fibre and glass fibre etc.；Auxiliary agent refers to carbon fiber sizing agent, basalt
Fiber and glass fiber infiltration agent.High-performance fiber interface modification auxiliary agent is the layer of surface processing coated for fiber surface
Agent not only determines the transaction capabilities of fiber, is also largely fixed the performance of fiber in the composite.Existing fiber circle
Face modified additive is usually the aqueous solution being made of film forming agent, coupling agent, antistatic agent, emulsifier etc. or lotion, can effectively be soaked
Moisten fiber surface, keeps fiber smooth, soft, wear-resisting and assign fiber surface certain activity, to keep fiber better
With resin-bonded.The effect of auxiliary agent is mainly manifested in the following aspects：Humidification, coheres boundling work at lubrication protection effect
With, prevent the accumulation of fiber surface electrostatic charge and high-performance fiber made to obtain with the good compatibility of resin matrix etc..Only
Under the action of auxiliary agent, could assign the physical properties such as the good mechanics of fibre, electricity and it is ageing-resistant etc. chemically
Energy.Most important composition is film forming agent in auxiliary agent, and other than playing enhancing and protective effect to fiber, it is hard to high-performance fiber
Stiffening property, convergence, choppability and wellability play a key effect and the performance in fiber later stage has effect of crucial importance.
Common auxiliary agent majority industrial at present is with PVAc lotions, acrylic acid ester emulsion, epoxy resin latex, polyurethane breast
Liquid and polyester emulsion etc. are used as main film-former, and PVAc lotions are cheap, but poor with resin matrix combination wellability；
Although epoxide resin type film forming agent technically apply it is more mature, be not suitable for other resin matrixes.Polyester resin is by more
First carboxylic acid（Or acid anhydrides）It is made by high temperature polycondensation with polyalcohol, polyester emulsion bonds glass monofilament as film forming agent
Convergence is good, since it and FRP (fibre reinforced composites) resin matrix are all unsaturated polyester (UP), the two chemical-physical parameters
Closely, so being infiltrated to high-performance fiber, yarn, cloth or felt fast.Unsaturated-resin matrix can be sent out in solidification with film forming agent
Raw cross-linking reaction generates integration solidification, therefore interface cohesion is good, and FRP product properties is preferable.
There are two types of the production methods of common polyester-type lotion domestic at present：Self-emulsification and outer emulsion process.Outer emulsion process：It will
Polyacid or acid anhydrides carry out sufficient polycondensation reaction at 200-220 °C with polyalcohol, and cooling down to be added after reaching theoretical acid value has
Then solvent, polymerization inhibitor and emulsifier pass through high speed shear, lotion are made by phase inversion.Self-emulsification is exactly not
Hydrophilic radical is introduced in saturated polyester, so that entire strand is formed amphiphilic polymers, can be served as the effect of emulsifier, this
Sample avoids additional emulsifier, and film forming agent is migrated with emulsifier during avoiding later stage fiber drying.According to hydrophilic expansion used
Polyester-type lotion can be divided into anionic, cationic and nonionic by the type of chain agent.
The method that the polyester fiber type size that Chinese patent CN104530405A is announced uses is binary acid and dihydric alcohol
High temperature carries out polycondensation reaction, and appropriate unsaturated dibasic acid is added after acid value declines to a certain extent or acid anhydrides continues instead
It answers, is emulsified when acid value drops to 30 or less.The molecular weight of polyesters that the invention obtains is low, and particle size distribution is uneven,
It can not meet actual production requirement, additionally needing the outer emulsifier of addition could emulsify, fiber table during later stage fiber drying
Face film forming agent will produce migration with water evaporation, be embodied in fiber it is coiled after in the drying process due to the migration of film forming agent,
Fiber inner wrap layers, centre circle and outer layer film former content are different, and stability of emulsion is also poor in addition.
Chinese patent CN101831078A discloses a kind of manufacturing method of film forming agent and the size containing the film forming agent,
Specific to describe binary acid or acid anhydrides and glycol monomer progress polymerisation, 72 ~ 87mgKOH/g of endpoint acid number obtains carboxyl
The polyester of sealing end.The linear epoxy resin of both-end epoxy group is added, the epoxy group and polyester end carboxyl for making 35% ~ 55% are opened
Ring graft reaction, acid value drop to 1mgKOH/g or less.The aminated compounds containing active hydrogen on nitrogen-atoms is added, with residue ring
Oxygen groups ring-opening reaction is added organic acid and generates cationic polymer later.The endpoint acid number of the invention first step is too high, molecule
Measure it is low, later lean on epoxy resin carry out open loop chain extension, since epoxy resin reaction temperature be added is too high, under 130-150 °C
The epoxy group of epoxy resin but also can not only react, it is difficult to control polymerization with intramolecular hydroxyl reaction with polyester end carboxyl
Object is reacted according to design direction, causes generated polymer to generate branched, and molecular weight distribution broadens, and it is anti-that gelation occurs when serious
It answers.
Invention content
For the collection of filaments and bad and bad with the resin compatible problem of fiber fiber separation, present invention aims at
A kind of preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive is provided.
Another object of the present invention is：It is fine to provide a kind of self assembly self-emulsifying self-stabilization polyester-type prepared by the above method
Tie up interface modification Additives Products.
Another object of the present invention is to：A kind of application of the said goods is provided.
The object of the invention is realized by following proposal：A kind of modification of self assembly self-emulsifying self-stabilization polyester-type fiber interface helps
The preparation method of agent, it is characterised in that include the following steps：
（1）Dicarboxylic acids/or acid anhydrides and glycol monomer carry out polymerisation, when endpoint acid number is less than or equal to 10；
（2）Unsaturated dibasic acid/acid anhydrides is added after cooling, and the reaction was continued, controls endpoint acid number between 30-50mg KOH/g,
（3）For the dicarboxylic acids/or acid anhydrides of high reaction activity, merge above-mentioned（1）With（2）Single step reaction；
（4）Epoxy resin is added and catalyst is reacted, the end carboxyl of epoxy group and polyester is made to carry out open loop graft reaction,
When acid value drops to 5mg KOH/g or less；
（5）Acid anhydrides is added and carries out carboxylation reaction, generates hydrophilic chain extension carboxyl；
（6）Later be added salt forming agent in and carboxyl, be eventually adding deionized water and can be obtained with self assembly self-emulsifying self-stabilization
Polyester-type fiber interface modified additive.
Step（2）Endpoint acid number is controlled between 30 ~ 40mg KOH/g.
Step（3）The dicarboxylic acids/or acid anhydrides of the high reaction activity are succinic acid, adipic acid, tetrahydrophthalic anhydride, hexahydrobenzene
Acid anhydride.
Step（1）In, dicarboxylic acids or acid anhydrides are phthalic anhydride, M-phthalic acid, terephthalic acid (TPA), methyl tetrahydrochysene
Phthalic anhydride, hexahydro phthalic anhydride, hydrogenation M-phthalic acid, malonic acid, succinic acid, adipic acid, dodecanedioic acid；Dihydric alcohol
For ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, 1,6- hexylene glycols, diethylene glycol (DEG), dipropylene glycol, Isosorbide-5-Nitrae-
Cyclohexanol, neopentyl glycol；Dihydric alcohol is 2~1 with the molar ratio of dicarboxylic acids or acid anhydrides:1~2, reaction temperature is in 150 DEG C of elder generations
Reaction, prevents exothermic reaction and excessive alcohol drain evaporation, is then warming up to 200-210 DEG C of progress esterification.
Dihydric alcohol is 1 with the molar ratio of dicarboxylic acids or acid anhydrides:1~0.5；Best acid value is less than 5mg KOH/g.
Step（2）Described in unsaturated dibasic acid or acid anhydrides be maleic anhydride, fumaric acid anhydride, itaconic acid, tetrahydrophthalic anhydride；No
Monounsaturated dicarboxylic acid or acid anhydrides proportion are that dihydric alcohol molal quantity subtracts rubbing for binary acid or acid anhydrides shown in claim 4 or 5
You multiply the factor that feeds intake by number, and the factor that feeds intake is defined as 2.5~1, most preferably tends to 2~1；Reaction temperature is stepped up to from 80 DEG C
210 DEG C, acid value declines very slow rear stopping and reacts and start to cool down.
Step（4）Epoxy resin is bisphenol A type epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, aliphatic
Linear epoxy resin, amine-modified epoxy resin；Reaction temperature is 100~120 DEG C, most preferably tends to 110~115 DEG C, is added
The epoxy resin equivalent of epoxy resin is 100 ~ 1000.
Step（4）Selected catalyst is nitrogenous and phosphorus compound or metal salt or complex compound such as tertiary amine, quaternary ammonium salt, three alkane
Base phosphorus, quaternary alkylphosphonium salts, addition are the 0.01% ~ 0.5% of total reactant weight.
Step（5）The acid anhydrides of addition is methyl tetrahydro phthalic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, tetrabromophthalic anhydride or methyl
The molal quantity of hexahydrophthalic anhydride, shared addition is calculated according to the hydroxyl value of polyester, and circular is:The molecular weight of acid anhydrides ×（It is poly-
The hydroxyl value of ester × polyester quality）/ (1000 × 56.1), reaction temperature are 100 ~ 150 DEG C, and the reaction time is 1 ~ 3 hour.
Step（6）Middle salt forming agent be added such as amine is primary amine, secondary amine or tertiary amine, and the salt forming agent molal quantity being added is equal to step
Suddenly（5）The molal quantity of middle acid anhydrides be added；Addition temperature is room temperature~100 DEG C, 0.5 ~ 1 hour reaction time.
The present invention provides a kind of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive, according to any of the above-described
The method is prepared.
A kind of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive of present invention offer is modified in fiber interface
The middle application as modified additive.
The controllable Nano type polyester emulsion of particle size can be made by this method, the design of molecule can be passed through in addition
To adjust the hydrophilic and lipophile of polyester.Polyester emulsion film forming agent is not only suitable for the production of carbon fiber sizing agent, can also use
In the production of basalt fibre and glass fibre interface modification size, while the glass transition of control film forming agent can be passed through
Temperature and soft or hard degree are to meet application demand of the fiber in different moulding process.The fiber interface prepared using the present invention is changed
Property auxiliary agent, can effectively solve the problems such as collection of filaments and fiber fiber separation are bad and bad with resin compatible, and breast
Liquid stability is resolved, and half a year is stored under room temperature, and there is no precipitate.
The present invention synthesizes the unsaturated polyester (UP) blocked containing end carboxyl first, and it is anti-that epoxy resin progress open loop chain extension is added later
Answer, further increase molecular weight, then to hydroxyl carry out carboxylation reaction, formed amphiphilic polyester, later be added salt forming agent into
Row neutralizes, and finally plus water obtains polyester-type fiber interface modified additive lotion.Emulsion particle diameter size can control, particle size
Between 20-150 nanometers.Film forming agent molecular weight can control molecular weight to be suitable for different high property between 3000~20000
It can fiber.The particle size and emulsion intercalation method of product lotion can be adjusted by adjusting hydrophilic chain extender proportion, by
Then self-emulsification approach is used to synthesize, storage stability is good at room temperature, not will produce precipitation in half a year.Additionally by using acid
The type of acid anhydride or epoxy resin may be controlled to the soft or hard of film, select aromatic acid or acid anhydrides synthesizing polyester and bisphenol-A type
Epoxy resin, which carries out chain extending reaction, can make film forming agent partially hard, if selecting aliphatic dibasic acid or acid anhydrides synthesizing polyester and fat
It is partially softer that type epoxy resin carries out chain extending reaction, that is, film forming agent.By the way that the compoundings such as lubricant, coupling agent and antistatic agent are added
Fiber sizing agent/the size made can efficiently control fiber filoplume amount and convergence, and fiber is imitated with resin-bonded
Fruit is fine.Since additive latex does not add organic solvent and emulsifier, sizing agent/size is coated in fiber drying after fiber
When, the migration of film forming agent greatly reduces, and fiber homogenizes and the intensity of fiber significantly improves, while optimizing fiber and matrix
The interface performance of resin effectively improves the performances such as composite material strength and service life.
Specific implementation mode
Embodiment 1：
46.02 grams of dipropylene glycol, 40.83 g of adipic acid, 8.4 grams of maleic anhydrides, two are added in 250 milliliters of reaction kettles
Gradually temperature reaction under carbonoxide atmosphere, the reaction at 200-210 DEG C is until acid value stops reaction after dropping to 38.Protective gas changes
Delay to 10.80 grams of addition bisphenol-A type epoxy resin, 0.10 gram of catalyst after 100 DEG C at nitrogen and hypothermic response temperature in the kettle
It is slow to be warming up to 110 DEG C the reaction was continued two hours, it is then warming up to 115 DEG C of reactions again until when acid value drops to 5 or less, is added
9.1 grams of methyl tetrahydro phthalic anhydride reacts two at 120 DEG C and as a child cooled to 85 DEG C of 7.5 grams of triethylamines of addition, and finally plus water carries out
Emulsification.
Embodiment 2：
78 grams of dipropylene glycol, 68.05 grams of adipic acid, 14.02 grams of maleic anhydride, two are added in 1000 milliliters of reaction kettles
200-210 DEG C is gradually warming up under carbonoxide atmosphere to be reacted.Stop reacting when acid value drops to 40 and cools to 100
DEG C, 0.1 gram of 19.6 grams of bisphenol A type epoxy resin and catalyst are added in a nitrogen atmosphere.It is reacted at 110-115 DEG C, works as acid value
18 grams of methyl tetrahydro phthalic anhydride is added when dropping to 5 or less.After being reacted 2 hours at 120 DEG C, cooling degree is to being added three second after 85 DEG C
10.83 grams of amine, finally plus water is emulsified, you can obtains the polyester-type emulsion film forming agent that acid value is 40.
Embodiment 3：
50.31 grams of the dipropylene glycol of addition in 500 milliliters of reaction kettles, 40.83 grams of adipic acid, 8.43 grams of maleic anhydride,
200-210 DEG C is gradually warming up under carbon dioxide atmosphere to be reacted, until acid value stops reaction after dropping to 35.In nitrogen atmosphere
0.08 gram of 9.45 grams of lower addition bisphenol A type epoxy resin and catalyst work as acid value after reacting two hours at 110-115 DEG C
7.23 grams of methyl tetrahydro phthalic anhydride is added when dropping to 5 or less and is added three after cooling to 85 DEG C after being reacted 2 hours at 120 DEG C
4.54 grams of ethamine, finally plus water is emulsified, you can obtains the polyester-type emulsion film forming agent that acid value is 35.
Embodiment 4：
85.5 grams of the dipropylene glycol of addition in 500 milliliters of reaction kettles, 58.05 grams of adipic acid, 14.04 grams of maleic anhydride,
200-210 DEG C of reaction is gradually warming up under carbon dioxide atmosphere until acid value stops reaction after dropping to 36.Protective gas changes into
18.12 grams of bisphenol A type epoxy resin, 0.15 gram of catalyst is added in nitrogen after cooling to 100 DEG C.Slowly it is warming up to 110 DEG C instead
Two hours are answered, three hours of 115 DEG C of reactions is then warming up to again until when acid value drops to 5 or less, methyl tetrahydrochysene benzene is added
15.02 grams of acid anhydride reacts two at 120 DEG C and as a child then cools to 85 DEG C, 9.14 grams of triethylamine is added, and finally plus water carries out
Emulsification.
Embodiment 5：
84.84 grams of the dipropylene glycol of addition in 500 milliliters of reaction kettles, 69.79 grams of adipic acid, 14.0 grams of maleic anhydride,
200-210 DEG C of reaction is gradually warming up under carbon dioxide atmosphere until acid value stops reaction after dropping to 30.Protective gas changes into
11.83 grams of bisphenol A type epoxy resin, 0.15 gram of catalyst is added in nitrogen after cooling to 100 DEG C.Slowly it is warming up to 110 DEG C instead
Two hours are answered, three hours of 115 DEG C of reactions is then warming up to again until when acid value drops to 5 or less, methyl tetrahydrochysene benzene is added
12.03 grams of acid anhydride.Two hours are reacted at 120 DEG C, and 7.31 grams of triethylamine is added after cooling to 85 DEG C.Finally plus water is emulsified,
Since acid value is too small, obtained lotion storage has precipitation to generate in one week below later.
Embodiment 6：
43.35 grams of neopentyl glycol, 48.9 grams of adipic acid, 10.2 grams of maleic anhydride, in titanium dioxide are added in 500 milliliters of reaction kettles
200-210 DEG C of reaction is gradually warming up under carbon atmosphere until acid value drops to 36 reactions stopping.Protective gas changes nitrogen into, cooling
10.48 grams of bisphenol A type epoxy resin is added after to 100 DEG C, 0.1 gram of catalyst is slowly warming up to 110 DEG C of two hours of reaction,
Then it is warming up to three hours of 115 DEG C of reactions again until when acid value drops to 5 or less, 8.9 grams of methyl tetrahydro phthalic anhydride is added.
120 DEG C of two hours of reaction cool to 80 °C of 5.38 grams of triethylamines of addition, and finally plus water is emulsified.Obtain white emulsion.
Embodiment 7：
41.07 grams of neopentyl glycol, 46.53 grams of adipic acid, 9.66 grams of maleic anhydride, in dioxy are added in 500 milliliters of reaction kettles
Change and is gradually warming up to 200-210 DEG C of reaction under carbon atmosphere until acid value stops reaction after dropping to 33.Protective gas changes nitrogen into,
9.28 grams of bisphenol A type epoxy resin is added after cooling to 100 DEG C, it is two small to be slowly warming up to 110 DEG C of reactions for 0.1 gram of catalyst
When, it is then warming up to three hours of 115 DEG C of reactions again until when acid value drops to 5 or less, 7.93 grams of methyl tetrahydro phthalic anhydride is added.
Three hours are reacted at 110 DEG C, 4.58 grams of triethylamine is added after cooling to 85 DEG C, and finally plus water is emulsified.Obtain white breast
Liquid.
Embodiment 8：
45.9 grams of neopentyl glycol, 51.6 grams of adipic acid, 10.80 grams of maleic anhydride, in titanium dioxide are added in 500 milliliters of reaction kettles
200-210 DEG C of reaction is gradually warming up under carbon atmosphere until acid value stops reaction after dropping to 37.Protective gas changes nitrogen into,
11.04 grams of bisphenol A type epoxy resin, 0.1 gram of catalyst are added after cooling to 100 DEG C.It is slowly warming up to 110 DEG C and reacts two
Hour, it is then warming up to three hours of 115 DEG C of reactions again until when acid value drops to 5 or less, methyl tetrahydro phthalic anhydride 9.45 is added
Gram.Two hours are reacted at 120 DEG C, 5.47 grams of triethylamine is added after cooling to 85 DEG C, and finally plus water is emulsified.It obtains white
Color lotion.
Claims (12)
1. a kind of preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive, it is characterised in that including such as
Lower step：
（1）Dicarboxylic acids/or acid anhydrides and glycol monomer carry out polymerisation, when endpoint acid number is less than or equal to 10；
（2）Unsaturated dibasic acid/acid anhydrides is added after cooling, and the reaction was continued, controls endpoint acid number between 30-50mg KOH/g,
（3）For the dicarboxylic acids/or acid anhydrides of high reaction activity, merge above-mentioned（1）With（2）Single step reaction；
（4）Epoxy resin is added and catalyst is reacted, the end carboxyl of epoxy group and polyester is made to carry out open loop graft reaction,
When acid value drops to 5mg KOH/g or less；
（5）Acid anhydrides is added and carries out carboxylation reaction, generates hydrophilic chain extension carboxyl；
（6）Later be added salt forming agent in and carboxyl, be eventually adding deionized water and can be obtained with self assembly self-emulsifying self-stabilization
Polyester-type fiber interface modified additive.
2. the preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive as described in claim 1, special
Sign is, step（2）Endpoint acid number is controlled between 30 ~ 40mg KOH/g.
3. the preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive as described in claim 1, special
Sign is, step（3）The dicarboxylic acids/or acid anhydrides of the high reaction activity are succinic acid, adipic acid, tetrahydrophthalic anhydride, hexahydrobenzene
Acid anhydride.
4. the preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive as described in claim 1, special
Sign is, step（1）In, dicarboxylic acids or acid anhydrides are phthalic anhydride, M-phthalic acid, terephthalic acid (TPA), methyl tetrahydrochysene
Phthalic anhydride, hexahydro phthalic anhydride, hydrogenation M-phthalic acid, malonic acid, succinic acid, adipic acid, dodecanedioic acid；Dihydric alcohol
For ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, 1,6- hexylene glycols, diethylene glycol (DEG), dipropylene glycol, Isosorbide-5-Nitrae-
Cyclohexanol, neopentyl glycol；Dihydric alcohol is 2~1 with the molar ratio of dicarboxylic acids or acid anhydrides:1~2, reaction temperature is in 150 DEG C of elder generations
Reaction, prevents exothermic reaction and excessive alcohol drain evaporation, is then warming up to 200-210 DEG C of progress esterification.
5. the preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive as claimed in claim 4, special
Sign is that dihydric alcohol is 1 with the molar ratio of dicarboxylic acids or acid anhydrides:1~0.5；Best acid value is less than 5mg KOH/g.
6. the preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive as described in claim 1, special
Sign is, step（2）Described in unsaturated dibasic acid or acid anhydrides be maleic anhydride, fumaric acid anhydride, itaconic acid, tetrahydrophthalic anhydride；No
Monounsaturated dicarboxylic acid or acid anhydrides proportion are that dihydric alcohol molal quantity subtracts rubbing for binary acid or acid anhydrides shown in claim 4 or 5
You multiply the factor that feeds intake by number, and the factor that feeds intake is defined as 2.5~1, most preferably tends to 2~1；Reaction temperature is stepped up to from 80 DEG C
210 DEG C, acid value declines very slow rear stopping and reacts and start to cool down.
7. the preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive as described in claim 1, special
Sign is, step（4）Epoxy resin is bisphenol A type epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, aliphatic line
Property epoxy resin, amine-modified epoxy resin；Reaction temperature is 100~120 DEG C, most preferably tends to 110~115 DEG C, ring be added
The epoxy resin equivalent of oxygen resin is 100 ~ 1000.
8. the preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive as described in claim 1, special
Sign is, step（4）Selected catalyst is nitrogenous and phosphorus compound or metal salt or complex compound such as tertiary amine, quaternary ammonium salt, three alkane
Base phosphorus, quaternary alkylphosphonium salts, addition are the 0.01% ~ 0.5% of total reactant weight.
9. the preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive as described in claim 1, special
Sign is, step（5）The acid anhydrides of addition is methyl tetrahydro phthalic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, tetrabromophthalic anhydride or methyl
The molal quantity of hexahydrophthalic anhydride, shared addition is calculated according to the hydroxyl value of polyester, and circular is:The molecular weight of acid anhydrides ×（It is poly-
The hydroxyl value of ester × polyester quality）/ (1000 × 56.1), reaction temperature are 100 ~ 150 DEG C, and the reaction time is 1 ~ 3 hour.
10. the preparation method of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive as described in claim 1, special
Sign is, step（6）Middle salt forming agent be added such as amine is primary amine, secondary amine or tertiary amine, salt forming agent molal quantity being added etc.
In step（5）The molal quantity of middle acid anhydrides be added；Addition temperature is room temperature~100 DEG C, 0.5 ~ 1 hour reaction time.
11. a kind of self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive, it is characterised in that according to claim 1 to
10 any one the method is prepared.
12. it is a kind of according to self assembly self-emulsifying self-stabilization polyester-type fiber interface modified additive described in claim 11 in fiber circle
Application in the modification of face as modified additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810198746.6A CN108484891B (en) | 2018-03-12 | 2018-03-12 | Preparation of self-assembly self-emulsifying self-stabilizing polyester type high-performance fiber interface modification auxiliary agent, product and application |
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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 |
| CN115746244A (en) * | 2022-11-23 | 2023-03-07 | 北京奥科瑞检测技术开发有限公司 | Super-wetting resin composition and preparation method thereof |
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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 |
| CN115746244A (en) * | 2022-11-23 | 2023-03-07 | 北京奥科瑞检测技术开发有限公司 | Super-wetting resin composition and preparation method thereof |
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