CN107312166B - A kind of modified PET polyester and its preparation method and application - Google Patents
A kind of modified PET polyester and its preparation method and application Download PDFInfo
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- CN107312166B CN107312166B CN201710509719.1A CN201710509719A CN107312166B CN 107312166 B CN107312166 B CN 107312166B CN 201710509719 A CN201710509719 A CN 201710509719A CN 107312166 B CN107312166 B CN 107312166B
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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
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
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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
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to a kind of modified PET polyesters and its preparation method and application, belong to modified poly ester field.Modified PET polyester includes aerogel particle and polyethylene terephthalate, and aerogel particle is dispersed in the molecule interchain of polyethylene terephthalate；The grain size of aerogel particle is 23 μm, and the content in modified PET polyester is 1 10wt%.Aerosol powder is added in ethylene glycol to be placed in grinder and is ground, mixed serum is made, esterification and polymerisation are carried out after mixed serum is mixed with terephthalic acids, modified PET is made.Modified PET slice-metering-spinneret-cooling-oil-is stretched into-thermal finalization-winding shaping, modified PET fiber is made.The present invention introduces aerogel particle, modified PET good spinnability obtained before PET polyesters, and the modified PET fiber that can produce various thicknesses has a wide range of application, and can meet the production needs of various fabrics.
Description
Technical field
The invention belongs to modified poly ester fields, and in particular to a kind of aeroge modified PET polyester and preparation method thereof and answer
With.
Background technology
Terylene (PET fiber) is world wide production maximum, and most widely used synthetic fibers kind, it is fine that terylene accounts for world's synthesis
Tie up 60% or more of yield.It is largely used to the textiles such as dress material, bedding, various trimming cloth, defence and military particular fabric
And other industrial fibre products, such as filtering material, insulating materials, tire cord, conveyer belt.As domestic economy is held
The demand of the continuous improvement of continuous rapid growth and domestic consumption of resident ability, domestic area polyester staple fiber also constantly increases.
Chinese Polyester Series product production capacity increases with surprising rapidity, and polyester fiber production capacity increases rapidly so that China is just gradual
Develop into the important processing base of world's terylene class product.
Aeroge is also known as blue smoke, is a kind of light porous amorphous inorganic nano material of structure-controllable, has continuous three
Reticular structure is tieed up, porosity is up to 80%~99.8%, and bore hole size is 1~100nm, 200~1000 ㎡ of high-specific surface area/
G, 50~100kg/m of low-density variation range3, thermal coefficient is less than 0.016~0.022W/ (mK) under normal temperature and pressure, than quiet
Only the thermal conductivity 0.026W/ (mK) of air is also low, is the minimum solid material of current thermal conductivity.
Conventional polyester fiber exist do not absorb water, dyeability is poor, dress is uncomfortable and it is easy catch fire with it is combustion-supporting etc. scarce
Point.The prior art prepares flame-resistant terylene to improve terylene the shortcomings that easily catching fire with combustion-supporting aspect using halogen modified terylene
Fiber, this method can make terylene have a flame retardant effect, but it is whole the production cost increases by about one time, be not suitable for extensive life
Production and popularization and application.
Application No. is 201310347276.2 Chinese patents to add aeroge to improve the heat-insulating property of polyester fiber
Enter into fiber and be modified, has main steps that and mix aerogel powder and fluoropolymer resin, the mixing granulator in kneading machine；It will mix
Refining is granulated obtained master batch melt-out spinning, obtains synthetic fibers.But this method preparation drops to the thermal coefficient of synthetic fibers
0.015-0.02w/m.k or so greatly reduces material thermal conductivity, and the heat-insulating property of synthetic fibers is made to be improved significantly.
But will appear when directly mixing aerogel powder and fluoropolymer resin mixing it is uneven problem, will appear in follow-up spinning
The problem of tensile strength reduces, easy fracture of wire and lousiness are typically only capable to produce thicker fiber, limit large-scale application.
The Chinese invention patent application of Publication No. CN102557577A provides a kind of aerosil composite wood
The preparation of material and method, using ethyl orthosilicate as silicon source, the glass fibre or fiber cotton material of industrialized production as reinforcement,
Obtained silicon dioxide silica aerogel composite material has high porosity, high-specific surface area, low-density, low-k and low-heat
The characteristics such as conductance have good mouldability, but ethyl orthosilicate is toxic and expensive, and silicon alkoxide is suitble to work as silicon source
Industry produces.
Therefore, how the excellent aeroge of processability, and it is to need at present that this aeroge, which effectively applied in PET fiber,
Technical problems to be solved.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of aeroge modified PET polyester and its preparation sides
Method and application.Terephthalic acid (TPA) is added after aerogel powder to be added to the particle that grinding grain size is 2-3 μm in ethylene glycol in the present invention,
Direct polymerization is at modified PET polyester, so that aerogel particle is dispersed in the molecule of polyethylene terephthalate
Interchain；And the present invention introduces aerogel particle, simple production process before PET polyesters.The modified PET fiber of the present invention removes
Outside good characteristic with PET fiber itself, the effect in terms of fire-retardant, ventilative and moisture absorbing and sweat releasing property is also obviously improved.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of modified PET polyester, the modified PET polyester include aerogel particle and polyethylene terephthalate,
The aerogel particle is dispersed in the molecule interchain of polyethylene terephthalate；Aerogel particle is poly- in modified PET
Content in ester is 1-10wt%；The grain size of aerogel particle is 2-3 μm；
The aerogel particle is aerogel particles.
The surface atom of nano-particle has unsaturated property there are many dangling bonds, thus easily with other atom phases
In conjunction with and tend towards stability, have very high chemism.For the system compound to modified PET polyester, the aggregation of nano-particle
Body is the smaller the better, and activeness and quietness effect is more apparent；The aggregation of nano-particle can be such that compound system loses when being more than certain size
Meaning.Therefore, in the preparation process of PET/ aerogel particle composite materials, how aeroge to be existed with nano-size dispersion
It is vital in polyethylene terephthalate (PET).The present invention is used aerogel powder being added in ethylene glycol and be ground
Mill, only after grinding the particle that grain size is 2-3 μm, aerogel particle uniform could be dispersed in ethylene glycol solution, subsequently
Terephthalic acid (TPA) is added, direct polymerization can be used as effective nucleating agent, improve crystallization at modified PET polyester, aerogel particle
Rate improves crystal property, simultaneously as aerogel particle is just dispersed in above-mentioned polymerization system before PET polyesters
In, therefore, after polymerisation so that aerogel particle is dispersed in the molecule interchain of polyethylene terephthalate, aeroge
The dispersion effect of particle is good, to while ensureing PET polyester excellent performance itself, come with aerogel particle composite band
Fire-retardant, heat-insulating property.
In addition, aerogel particles interior three-dimensional solid space structure plays an important roll the performance of its heat-insulating property,
In product preparation process binder or other materials enter its three-dimensional space block can make after porous structure its reduce or
Lose fire-retardant, heat-insulating property；The effect of ethylene glycol is wetting aerogel particles, and it is three-dimensional to occupy aerogel particles interior three-dimensional
The porous structure in space prevents binder or other materials in product preparation process porous into the closure of its three-dimensional space
Structure, after product drying, ethylene glycol volatilizees naturally, its three-dimensional space structure is still maintained inside aerogel particles, hair
Wave fire-retardant, heat-insulating property.
As preferred technical solution：
Modified PET polyester as described above, the aerogel particle are using sodium metasilicate as the aerogel particle of silicon source；
Silica aerogel needs to prepare by silica aerogel presoma, and the preparation method of silica aerogel presoma is：
(1) mixed solution of silicon source and solvent is prepared
The sodium metasilicate for several 3.0-4.0 that rub is taken to be fitted into reaction kettle, the deionized water progress that 1-3 times of sodium metasilicate quality is added is dilute
It releases, reaction kettle is stirred 30 minutes with 80-200 revs/min of speed, through 200 mesh screens, obtains sodium silicate solution；Sodium metasilicate
Aqueous solution be commonly called as waterglass, it is made of the alkali metal and silica of different proportion, chemical formula R2O·
nSiO2, R in formula2O is alkali metal oxide, n is the ratio of silica and alkali metal oxide molal quantity, referred to as waterglass
Rub number, and the most commonly used is sodium silicate water glass Na2O·nSiO2；
(2) colloidal sol
It takes A sour, A acid metal salts is added in A acid and rare earth A hydrochlorates are added in a manner of spray to step after mixing
Suddenly the sodium silicate solution that (1) obtains；The material in reaction kettle is carried out soon with 1200-2000 revs/min of speed while spray
Speed stirring, the pH value for controlling sodium silicate solution is 1.5-3.0, obtains colloidal sol；
(3) gel
Sodium hydroxide or ammonium hydroxide are taken, it is 10-11.5 that deionized water, which is added, and is diluted to pH value, is added in a manner of spray to anti-
It answers in kettle；The material in reaction kettle is quickly stirred with 1200-2000 revs/min of speed while spray, works as reaction kettle
When the pH value of interior material is 4.5-5.5, spray is terminated, gel is obtained；
(4) aging
Stirring 3-10 hours is continued with 20-50 revs/min of speed in reaction kettle, aging is carried out to the material in reaction kettle,
It is 35-50 degrees Celsius to control material in reactor temperature；The mode that standing is usually used in the prior art carries out aging, takes 3
~5 days, gel can't be stirred, the reason is that the prior art needs to stand during generally believing aging, it is quiet
The structure growth of aeroge can be convenient for by setting；
(5) solvent is replaced
It carries out continuing stirring 60-180 minutes in reaction kettle, while being added same with aging material in step (4) reaction kettle
The displacement solvent of volume, to displace remaining moisture；The prior art worries that stirring can destroy its structure, will not generally replace
When be stirred, stewing process can be taken, cause take it is longer；Preparation method provided by the invention is stirred when solvent is replaced
60~180min is mixed, can greatly shorten period of a permutation, there is no destroyed microstructure；
(6) surface modification
It carries out continuing stirring in reaction kettle, while continuously adding and aging material same volume in step (4) reaction kettle
Coupling agent；By stirring 60-180 minutes, the aerogel precursor body for being coated with displacement solvent and coupling agent is obtained.Above-mentioned steps
(6) coupling agent that surface modification is added cements out the water in silica aerogel micropore, and coupling agent is filled into silica aerogel micropore
It is interior, the stability of microcellular structure can be improved, the evenness of pore size is improved；In addition, by different coupling agents is added
After being surface modified, silica aerogel hydrophobicity, hydrophilic sexual function can be adjusted.
Modified PET polyester as described above, in step (2), the A acid is sulfuric acid, hydrochloric acid, oxalic acid or nitric acid, spend from
Sub- water is adjusted to 6-15mol/L；The A acid metal salts are A acid zirconates or A acid aluminium salts；The rare earth A hydrochlorates are A acid cerium salt, A
Sour yttrium salt or A acid lanthanum salts；
In step (2), in terms of oxide, the molar ratio of the two is 100 for the A acid metal salts and rare earth A hydrochlorates:1-6；A
The molar ratio 2-5 of silica in the oxide and sodium metasilicate of acid metal salt:100；A acid metal salts and rare earth A hydrochlorates are easy the moisture absorption,
Metering can be caused inaccurate, so for its addition of accurate quantitative analysis, A acid metal salts described in step (2) and rare earth A hydrochlorates with
The molar ratio of oxide meter, the two is 100：1~6；Silica in the oxide of A acid metal salts and sodium metasilicate B in step (2)
Molar ratio 2~5：100；For example, A acid metal salts are aluminum sulfate, in terms of its oxide, i.e., to be aoxidized in aluminium oxide and sodium metasilicate B
The molar ratio of silicon is 2~5：100；
In step (5), the displacement solvent is one or more of methanol, acetone, n-hexane or heptane；Step (5)
Or the stirring described in step (6) is that heart offer is quickly forward stirred in a kettle, the periphery at reaction kettle center provides folding
Flowing plate；
Coupling agent described in step (6) is hexamethyldisilazane, bis- (trimethylsilyl) acetamides, methoxyl group trimethyl silicane
Alkane, dimethoxydimethylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxysilane, first
One or more of ethyl triethoxy silicane alkane or methyl trimethoxy oxygroup alkane.
The aerogel precursor body is prepared using normal temperature and pressure technique productions, is a kind of the light porous non-of structure-controllable
There is crystalline inorganic nano material continuous tridimensional network, porosity to be up to 80% or more, and average pore size is 20nm left
The right side, specific surface area are more than 500 ㎡/g, and density is less than 70kg/m3, thermal coefficient is less than 0.020W/ (mK) under normal temperature and pressure, than
The thermal conductivity 0.022W/ (mK) of still air is also low, be at present rare low cost, industrialization, low heat conductivity solid material
Material.
The silica aerogel presoma of preparation is put into drying kettle, is filled in drying kettle by modified PET polyester as described above
Nitrogen catches up with oxygen, until oxygen content is less than 3% in drying kettle, then carries out micro-wave vacuum to the material in drying kettle；It is dry
Negative pressure 0.08-0.12MPa in kettle, temperature are 85-135 DEG C, and the silica aerogel of solid powder is made after dry；
Aeroge produced by the present invention has following characteristic：1, several infinite more nano-pores are distributed in the inside of aeroge
And air vent wall, air can not be flowed freely in nanometer stomata, be relatively adsorbed on air vent wall, aerogel material is in class
Likelihood dummy status, effectively reduces convection current heat transfer, and heat is transmitted in solid material and can be transmitted along air vent wall；These air vent wall structures
At the heat conduction path of infinite length, this will substantially reduce heat conduction；2, there are infinite more air vent wall, gas inside aeroge
Hole wall is equivalent to infinite more thermal baffle, the reflection to light and heat may be implemented, to which radiant heat transfer be greatly lowered；3, gas
Gel can effectively penetrate sunlight, and prevent the infrared emanation of environment temperature, become a kind of ideal transparent heat-insulated material,
The thermal conductivity of material is set to substantially reduce；Aeroge is that only a few is provided simultaneously with effectively insulating, and waterproof is prevented fires, condensation-proof, sound insulation
Material, while there is good gas permeability.
As above the preparation method of any modified PET polyester, includes the following steps：
(1) aerosol powder is added in ethylene glycol and is placed in grinder and grinds, be made mixed serum, in mixed serum
Aerosol grain size is 2-3 μm；
(2) esterification and polymerisation are carried out after mixing mixed serum with terephthalic acids successively, modified polyphenyl is made
Dioctyl phthalate ethylene glycol fat, i.e. modified PET.
The preparation method of modified PET polyester as described above, the grinder are planetary-type grinding machine, the mill in grinder
Ball is the zirconia ball of a diameter of 0.5-1mm, milling time 15-30min, grinding rate 250-600rpm；Aerosol powder
The addition at end is the 8-15% of quality of glycol；The molar ratio of ethylene glycol and terephthalic acid (TPA) is 1:1-1.2；
Esterification is the compressive reaction in nitrogen atmosphere in step (2), and moulding pressure is normal pressure~0.3MPa, temperature
It is 250~260 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value, obtains
Modified ethylene glycol terephthalate；
Polymerisation is to start low vacuum under conditions of negative pressure under the action of catalyst and stabilizer in step (2)
The polycondensation reaction in stage, the staged pressure are steadily evacuated to absolute pressure 500Pa hereinafter, temperature control is 260~270 by normal pressure
DEG C, the reaction time is 30~50 minutes；It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to drop
It is less than 100Pa to absolute pressure, modified poly ester is made in 275~280 DEG C, 50~90 minutes reaction time in reaction temperature control.
The preparation method of modified PET polyester as described above, the catalyst are antimony oxide, antimony glycol or acetic acid
Antimony, catalyst charge are the 0.01%~0.05% of terephthalic acid (TPA) weight；The stabilizer is triphenyl phosphate, tricresyl phosphate
Methyl esters or Trimethyl phosphite, stabilizer addition are the 0.01%~0.05% of the terephthalic acid (TPA) weight.
The preparation method of modified PET polyester as described above, will be in modified PET slice-metering-spinneret-cooling-
Modified PET fiber is made in oil-stretching-thermal finalization-winding shaping.When preparing the modified PET fiber of the present invention, only need to use
The manufacture craft of existing PET.
The speed of the application of modified PET polyester as described above, winding shaping is 2500-2800m/min, the temperature of extrusion
It it is 280~290 DEG C, cooling wind-warm syndrome is 20~25 DEG C；A diameter of 13-17 μm of the modified PET fiber.
The thermal coefficient of modified PET fiber produced by the present invention can reach 0.035~0.046w/m.k, limit oxygen index
>=31.5% (《GB/T 5454-1997 textile combustion performance test oxygen index methods》), there is excellent flame retardant property；The fibre
Dimension is lighter 20-31% than general PET fiber, changes in quality from non-porous silk into the porous fibre containing 22-30 or more air, light in addition to having
Other than warm performance, it is also equipped with the functions comfortable and easy to wear such as ventilative and absorbing sweat.
Advantageous effect：
The present invention is used aerogel powder being added in ethylene glycol and be ground, only after grinding the particle that grain size is 2-3 μm,
Aerogel particle uniform could be dispersed in ethylene glycol solution, and terephthalic acid (TPA) is subsequently added, and direct polymerization is poly- at modified PET
Ester, aerogel particle can be used as effective nucleating agent, improve crystalline rate, improve crystal property, simultaneously as aeroge
Grain is just dispersed in before PET polyesters in above-mentioned polymerization system, therefore, after polymerisation so that aerogel particle uniformly divides
It is dispersed in the molecule interchain of polyethylene terephthalate, the dispersion effect of aerogel particle is good.
The modified PET fiber of the present invention is other than the good characteristic with PET fiber itself, in fire-retardant, ventilative and moisture absorption
The effect of perspiration wicking aspect is also obviously improved.
The modified PET good spinnability of the present invention, can not only produce thicker modified PET fiber, can also produce diameter
For 13-17 μm of thinner modified PET fiber, have a wide range of application, the production needs of various fabrics can be met.
The deionized water of wet concentration conductivity indices≤10 in the present invention reduces impurity and can save production cost；
Operation principle prepared by middle rare earth toughening aerogel precursor body (silica aerogel i.e. described herein) of the present invention is：Gas
In the preparation method of Gel Precursor, the A acid metal salts and rare earth A hydrochlorates being added in gel process can reach toughening and carry
The effect of high silica aerogel heat resistance；Aging and solvent swap step are carried out in the state of stirring, are substantially increased anti-
Efficiency is answered, the process time is had compressed, is suitble to industrialization；
Compared with prior art, advantage has the following to middle rare earth toughening aerogel precursor preparation of the present invention：
(1) in recent years, there are some about the relevant report and patent for preparing silica aerogel under room temperature differential pressure in the prior art
Document, but be to rest on laboratory preparatory phase mostly, technical process is longer, while process implementing narrow limits, it is difficult to real
Existing large-scale industrialized production and application；The present invention provides the preparation methods under normal temperature and pressure, and it is relatively quiet to change the prior art
Technique only applies in critical process process and stirs, speeded up to the hydrolysis, polycondensation and modification of aeroge, realized in 30h
The technique of synthesis gas Gel Precursor provides a kind of method that industrial batch prepares rare earth toughening silica aerogel, is silicon gas
A large amount of manufacture and use of gel provide premise；
(2) one of hinder the reason of aeroge development that be aeroge have reticular structure, but the structure in the prior art
Edge it is relatively thin, more crisp, compression strength is low, and easy compression is caved in, and causes performance unstable；Present invention addition rare earth A hydrochlorates
With A acid metal salts, the toughness of the material is improved, improves the intensity of silica aerogel；
(3) temperature in use of the silica aerogel of prior art preparation is relatively low, generally used below also relatively more steady at 500 DEG C
Fixed, 500 DEG C or more the internal structure changes that can lead to silica aerogel cause thermal coefficient to decline；The present invention is sour with rare earth A is added
Salt and A acid metal salts, improve the heat resistance of the material, improve the heat resisting temperature of silica aerogel.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
The preparation method of silica aerogel presoma is：
(1) mixed solution of silicon source and solvent is prepared
It takes several 3.0 waterglass that rub to be fitted into reaction kettle, the deionized water of 2.5 times of quality is used in combination to be diluted, 180 revs/min
Clock stirs 30 minutes, through 200 mesh screens, obtains water glass solution.
(2) colloidal sol
It takes 8mol/L sulfuric acid, sulfuric acid zirconates is added (sulfuric acid zirconates in terms of its zirconium oxide, with the silica of water glass solution
Molar ratio is 5:100), (for sulfuric acid yttrium salt in terms of its yttrium oxide, the molar ratio with aluminium oxide is 1 to sulfuric acid yttrium salt:100)；Mixing is equal
After even, spray is added the water glass solution obtained to step (1), and spray while is quickly stirred with 1300 revs/min of speed
It mixes, control ph is controlled to spray, spray time is stopped when 1.5 at 100 minutes；Obtain colloidal sol.
(3) gel
The sodium hydroxide solution for being 11 by pH value, spray are added into colloidal sol obtained by step (2), with 1300 while spray
Rev/min speed quickly stirred, until pH value be 5 when stop spray, 120 minutes used times, obtain gel.
(4) aging
Reaction kettle continues stirring 10 hours with 40 revs/min of speed to gel, and control reaction kettle inner gel temperature is taken the photograph for 45
Family name's degree.
(5) solvent is replaced
The displacement solvent hexane with the material same volume of aging, stirring 2 are added while being stirred in reaction kettle
Hour.
(6) surface modification
The coupling agent with the material same volume of aging is added in reaction kettle；The coupling agent is dimethoxy dimethyl-silicon
Alkane, by stirring 150 minutes, obtain being coated with the silica aerogel presoma of displacement solvent and coupling agent after surface modification.
The preparation method of solid-state aerogel particles, includes the following steps：The silicon of displacement solvent and coupling agent will be coated with
Aerogel precursor body carries out micro-wave vacuum, and nitrogen catches up with oxygen to oxygen content to be less than 3% in drying kettle, and negative pressure 0.08MPa, 95 take the photograph
Family name's degree, microwave frequency control in the range of 2450MHZ ± 10MHZ, the silica aerogel solid powder for obtaining toughening in 55 minutes.
After testing, average pore size 26nm, specific surface area is 588 ㎡/g, loose specific weight 0.057g/cm to product3, it is super-hydrophobic,
Fire-retardant, thermal coefficient 0.021W/MK, 880 DEG C of heat resisting temperature, compressive resistance 0.118MPa.
Embodiment 2
The preparation method of silica aerogel presoma is：
(1) mixed solution of silicon source and solvent is prepared
It takes several 3.2 waterglass that rub to be fitted into reaction kettle, the deionized water of 3 times of quality is used in combination to be diluted, 200 revs/min,
Stirring 30 minutes, through 200 mesh screens, obtains water glass solution.
(2) colloidal sol
Take 10mol/L nitric acid, be added hydrochloric acid aluminium salt (hydrochloric acid aluminium salt in terms of aluminium oxide, aluminium oxide and oxygen in water glass solution
The molar ratio of SiClx is 2:100), (for hydrochloric acid lanthanum salt in terms of lanthana, the molar ratio with aluminium oxide is 3 to hydrochloric acid lanthanum salt:100)；It is mixed
After closing uniformly, spray is added the water glass solution obtained to step (1), and spray while is carried out fast with 1200 revs/min of speed
Speed stirring, until 2.5, spray time was controlled at 100 minutes control ph；Obtain colloidal sol.
(3) gel
By the ammonia spirit of pH value 10.5, spray is added to colloidal sol obtained by step (2), with 1200 revs/min while spray
Speed quickly stirred, until pH value be 4.5 when stop spray, 150 minutes used times, obtain gel.
(4) aging
Reaction kettle continues stirring 5 hours with 30 revs/min of speed, and control reaction kettle inner gel temperature is 50 degrees Celsius；
(5) solvent is replaced
The displacement solvent methanol with the material same volume of aging is added while being stirred in reaction kettle, to displace
Remaining moisture.
(6) surface modification
The coupling agent with the material same volume of aging is added in reaction kettle；The coupling agent is vinyl trimethoxy silicon
Alkane obtained the silica aerogel presoma for being coated with displacement solvent and coupling agent after surface modification by stirring 100 minutes.
The preparation method of solid-state aerogel particles, includes the following steps：The silicon of displacement solvent and coupling agent will be coated with
Aerogel precursor body carries out micro-wave vacuum, and nitrogen catches up with oxygen to oxygen content to be less than 2% in drying kettle, negative pressure 0.09MPa, and 110
Degree Celsius, microwave frequency controls in the range of 2450MHZ ± 10MHZ, 50 minutes, obtains the silica aerogel solid-state powder of toughening
Body.
After testing, average pore size 28nm, specific surface area is 568 ㎡/g, loose specific weight 0.056g/cm to product3, it is super-hydrophobic,
Fire-retardant, thermal coefficient 0.0198W/MK, 920 DEG C of heat resisting temperature, compressive resistance 0.122MPa.
Embodiment 3
The preparation method of silica aerogel presoma is：
(1) mixed solution of silicon source and solvent is prepared
It takes several 4.0 waterglass that rub to be fitted into reaction kettle, the deionized water of 3 times of quality is used in combination to be diluted, 80 revs/min,
Stirring 30 minutes, through 200 mesh screens, obtains water glass solution.
(2) colloidal sol
15mol/L nitric acid is taken, oxalic acid aluminium salt is added, and (in terms of aluminium oxide, the molar ratio with silica in water glass solution is
3:100), (in terms of lanthana, the molar ratio with aluminium oxide is 6 to oxalic acid lanthanum salt:100)；After mixing, spray is added to step
(1) water glass solution obtained, spray while, are quickly stirred with 1800 revs/min of speed, and control ph is to 2.5
Only, spray time control was at 100 minutes；Obtain colloidal sol.
(3) gel
By the sodium hydroxide solution of pH value 11.5, spray is added to colloidal sol obtained by step (2), with 1200 while spray
Rev/min speed quickly stirred, until pH value be 5.5 when stop spray, 80 minutes used times, obtain gel.
(4) aging
Reaction kettle continues stirring 5 hours with 50 revs/min of speed, and control reaction kettle inner gel temperature is 35 degrees Celsius；
(5) solvent is replaced
The displacement solvent acetone with the material same volume of aging is added while being stirred in reaction kettle, to displace
Remaining moisture.
(6) surface modification
The coupling agent with the material same volume of aging is added in reaction kettle；The coupling agent is hexamethyldisilazane, double
(trimethylsilyl) acetamide, methoxytrimethylsilane weight respectively account for the mixture of one third, by stirring 180 minutes, table
The silica aerogel presoma for being coated with displacement solvent and coupling agent is obtained after the modification of face.
The preparation method of solid-state aerogel particles, includes the following steps：The silicon of displacement solvent and coupling agent will be coated with
Aerogel precursor body carries out micro-wave vacuum, and nitrogen catches up with oxygen to oxygen content to be less than 1% in drying kettle, and negative pressure 0.12MPa, 80 take the photograph
Family name's degree, microwave frequency control in the range of 2450MHZ ± 10MHZ, 60 minutes, obtain the silica aerogel solid powder of toughening.
After testing, average pore size 27nm, specific surface area is 575 ㎡/g, loose specific weight 0.058g/cm to product3, it is super-hydrophobic,
Fire-retardant, thermal coefficient 0.0202W/MK, 725 DEG C of heat resisting temperature, compressive resistance 0.125MPa.
Embodiment 4
The preparation method of silica aerogel presoma is：
(1) mixed solution of silicon source and solvent is prepared
It takes several 3.5 waterglass that rub to be fitted into reaction kettle, the deionized water of 2.5 times of quality is used in combination to be diluted, 120 revs/min
Clock stirs 30 minutes, through 200 mesh screens, obtains water glass solution.
(2) colloidal sol
6mol/L nitric acid is taken, nitric acid zirconates is added, and (in terms of zirconium oxide, the molar ratio with silica in water glass solution is 4:
100), (in terms of cerium oxide, the molar ratio with zirconium oxide is 4 to nitric acid cerium salt:100)；After mixing, spray is added to step
(1) water glass solution obtained, spray while, are quickly stirred with 2000 revs/min of speed, control ph until 5,
Spray time was controlled at 120 minutes；Obtain colloidal sol.
(3) gel
By the ammonia spirit of pH value 10.5, spray is added to colloidal sol obtained by step (2), with 1300 revs/min while spray
Speed quickly stirred, until pH value be 4.5 when stop spray, 180 minutes used times, obtain gel.
(4) aging
Reaction kettle continues stirring 8 hours with 20 revs/min of speed, and control reaction kettle inner gel temperature is 40 degrees Celsius；
(5) solvent is replaced
Displacement solvent (acetone, the n-hexane with the material same volume of aging are added while being stirred in reaction kettle
And heptane, weight respectively account for the mixture of one third), to displace remaining moisture.
(6) surface modification
The coupling agent with the material same volume of aging is added in reaction kettle；The coupling agent be phenyl triethoxysilane,
Phenyltrimethoxysila,e, methyl trimethoxy oxygroup alkane weight respectively account for the mixture of one third, and by stirring 60 minutes, surface was repaiied
The silica aerogel presoma for being coated with displacement solvent and coupling agent is obtained after decorations.
The preparation method of solid-state aerogel particles, includes the following steps：The silicon of displacement solvent and coupling agent will be coated with
Aerogel precursor body carries out micro-wave vacuum, and nitrogen catches up with oxygen to oxygen content to be less than 3% in drying kettle, negative pressure 0.10MPa, and 100
Degree Celsius, microwave frequency controls in the range of 2450MHZ ± 10MHZ, 30 minutes, obtains the silica aerogel solid-state powder of toughening
Body.
After testing, average pore size 24nm, specific surface area is 558 ㎡/g, loose specific weight 0.061g/cm to product3, it is super-hydrophobic,
Fire-retardant, thermal coefficient 0.0196W/MK, 729 DEG C of heat resisting temperature, compressive resistance 0.121MPa.
Embodiment 5
A kind of preparation method of modified PET polyester, includes the following steps：
(1) ethylene glycol is added in the nano-titanium oxide for preparing embodiment 1 and the silica aerogel powder of rare earth solid solution bluk recombination
In after, be placed in grinder and grind, mixed serum is made, aerosol grain size after grinding in mixed serum is 2 μm；Grinder is
Planetary-type grinding machine, the abrading-ball in grinder are the zirconium balls of a diameter of 0.5mm, milling time 15min, and grinding rate is
250rpm；The addition of aerosol powder is the 8% of quality of glycol；
(2) esterification and polymerisation are carried out after mixing mixed serum with terephthalic acids successively, modified polyphenyl is made
Dioctyl phthalate ethylene glycol fat, i.e., compound PET.Wherein, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 1:1；Esterification is anti-in step (2)
Should be the compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure, and temperature is 250 DEG C, when the water quantity of distillate in esterification
It is esterification terminal when reaching 90% or more of theoretical value, obtains modified ethylene glycol terephthalate；
Polymerisation is under the action of catalyst and stabilizer in step (2), and catalyst is antimony oxide, catalyst
Addition is the 0.01% of terephthalic acid (TPA) weight；Stabilizer is triphenyl phosphate, and stabilizer addition is terephthalic acid (TPA)
The 0.01% of weight.Start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to by normal pressure
For absolute pressure 500Pa hereinafter, temperature control is at 260 DEG C, the reaction time is 30 minutes；It then proceedes to vacuumize, carries out high vacuum
The polycondensation reaction in stage makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature control is at 275 DEG C, the reaction time 50
Minute, modified PET polyester is made.
Embodiment 6
A kind of preparation method of modified PET polyester, includes the following steps：
(1) ethylene glycol is added in the nano-titanium oxide for preparing embodiment 2 and the silica aerogel powder of rare earth solid solution bluk recombination
In after, be placed in grinder and grind, mixed serum is made, aerosol grain size after grinding in mixed serum is 1 μm；Grinder is
Planetary-type grinding machine, the abrading-ball in grinder are the zirconium balls of a diameter of 1mm, milling time 20min, and grinding rate is
600rpm；The addition of aerosol powder is the 15% of quality of glycol；
(2) esterification and polymerisation are carried out after mixing mixed serum with terephthalic acids successively, modified polyphenyl is made
Dioctyl phthalate ethylene glycol fat, i.e., compound PET.Wherein, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 1:1.2；Esterification in step (2)
Reaction is the compressive reaction in nitrogen atmosphere, and moulding pressure 0.3MPa, temperature is 260 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching 90% of theoretical value or more, obtains modified ethylene glycol terephthalate；
Polymerisation is under the action of catalyst and stabilizer in step (2), and catalyst is antimony glycol, and catalyst adds
Enter 0.05% that amount is terephthalic acid (TPA) weight；Stabilizer is trimethyl phosphate, and stabilizer addition is terephthalic acid (TPA) weight
The 0.05% of amount.Start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolutely by normal pressure
To pressure 500Pa hereinafter, temperature control is at 270 DEG C, the reaction time is 50 minutes；It then proceedes to vacuumize, carries out high vacuum rank
The polycondensation reaction of section makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature is controlled at 280 DEG C, and the reaction time 90 divides
Modified PET polyester is made in clock.
Embodiment 7
A kind of preparation method of modified PET polyester, includes the following steps：
(1) ethylene glycol is added in the nano-titanium oxide for preparing embodiment 3 and the silica aerogel powder of rare earth solid solution bluk recombination
In after, be placed in grinder and grind, mixed serum is made, aerosol grain size after grinding in mixed serum is 2.5 μm；Grinder
For planetary-type grinding machine, the abrading-ball in grinder is the zirconium ball of a diameter of 0.8mm, milling time 18min, and grinding rate is
1500rpm；The addition of aerosol powder is the 10% of quality of glycol；
(2) esterification and polymerisation are carried out after mixing mixed serum with terephthalic acids successively, modified polyphenyl is made
Dioctyl phthalate ethylene glycol fat, i.e., compound PET.Wherein, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 1:1.1；Esterification in step (2)
Reaction is the compressive reaction in nitrogen atmosphere, and moulding pressure 0.2MPa, temperature is 255 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching 90% of theoretical value or more, obtains modified ethylene glycol terephthalate；
Polymerisation is under the action of catalyst and stabilizer in step (2), and catalyst is antimony acetate, and catalyst is added
Amount is the 0.03% of terephthalic acid (TPA) weight；Stabilizer is Trimethyl phosphite, and stabilizer addition is terephthalic acid (TPA) weight
The 0.04% of amount.Start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolutely by normal pressure
To pressure 500Pa hereinafter, temperature control is at 265 DEG C, the reaction time is 40 minutes；It then proceedes to vacuumize, carries out high vacuum rank
The polycondensation reaction of section makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature is controlled at 275~280 DEG C, reaction
Between 50~90 minutes, be made modified PET polyester.
Embodiment 8
A kind of preparation method of modified PET polyester, includes the following steps：
(1) ethylene glycol is added in the nano-titanium oxide for preparing embodiment 4 and the silica aerogel powder of rare earth solid solution bluk recombination
In after, be placed in grinder and grind, mixed serum is made, aerosol grain size after grinding in mixed serum is 2.2 μm；Grinder
For planetary-type grinding machine, the abrading-ball in grinder is the zirconium ball of a diameter of 0.8mm, milling time 28min, and grinding rate is
400rpm；The addition of aerosol powder is the 12% of quality of glycol；
(2) esterification and polymerisation are carried out after mixing mixed serum with terephthalic acids successively, modified polyphenyl is made
Dioctyl phthalate ethylene glycol fat, i.e., compound PET.Wherein, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 1:1.2；Esterification in step (2)
Reaction is the compressive reaction in nitrogen atmosphere, and moulding pressure 0.1MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching 90% of theoretical value or more, obtains modified ethylene glycol terephthalate；
Polymerisation is under the action of catalyst and stabilizer in step (2), and catalyst is antimony oxide, catalyst
Addition is the 0.04% of terephthalic acid (TPA) weight；Stabilizer is triphenyl phosphate, and stabilizer addition is terephthalic acid (TPA)
The 0.03% of weight.Start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to by normal pressure
For absolute pressure 500Pa hereinafter, temperature control is at 266 DEG C, the reaction time is 35 minutes；It then proceedes to vacuumize, carries out high vacuum
The polycondensation reaction in stage makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature control is at 276 DEG C, the reaction time 70
Minute, modified PET polyester is made.
Embodiment 9
A kind of preparation method of modified PET polyester fiber, includes the following steps：
Modified PET polyester slice-metering-spinneret-cooling-prepared by embodiment 5 oil-is stretched-heat is fixed
Modified PET fiber is made in type-winding shaping.Wherein, the speed of winding shaping is 2700m/min, the temperature of extrusion is 280~
290 DEG C, cooling wind-warm syndrome is 23 DEG C；
A diameter of 11 μm through modified PET fiber made from the above method.The thermal coefficient of modified PET fiber can reach
0.042w/m.k, limit oxygen index 31.9%, modified PET fiber of the invention have excellent flame retardant property；The fiber ratio
The light 20-31% of general PET fiber, changes in quality from non-porous silk at the porous fibre containing 22-30 or more air, in addition to having light and warm property
Other than energy, it is also equipped with the functions comfortable and easy to wear such as ventilative and absorbing sweat.
Embodiment 10
A kind of preparation method of modified PET polyester fiber, includes the following steps：
Modified PET polyester slice-metering-spinneret-cooling-prepared by embodiment 6 oil-is stretched-heat is fixed
Modified PET fiber is made in type-winding shaping.Wherein, the speed of winding shaping is 2500m/min, and the temperature of extrusion is 280
DEG C, cooling wind-warm syndrome is 20 DEG C；
A diameter of 11 μm through modified PET fiber made from the above method.The thermal coefficient of modified PET fiber can reach
0.035w/m.k, limit oxygen index 31.5%, modified PET fiber of the invention have excellent flame retardant property；The fiber ratio
The light 20-31% of general PET fiber, changes in quality from non-porous silk at the porous fibre containing 22-30 or more air, in addition to having light and warm property
Other than energy, it is also equipped with the functions comfortable and easy to wear such as ventilative and absorbing sweat.
Embodiment 11
A kind of preparation method of modified PET polyester fiber, includes the following steps：
Modified PET polyester slice-metering-spinneret-cooling-prepared by embodiment 7 oil-is stretched-heat is fixed
Modified PET fiber is made in type-winding shaping.Wherein, the speed of winding shaping is 2800m/min, and the temperature of extrusion is 290
DEG C, cooling wind-warm syndrome is 25 DEG C；
A diameter of 17 μm through modified PET fiber made from the above method.The thermal coefficient of modified PET fiber can reach
0.046w/m.k, limit oxygen index 32.3%, modified PET fiber of the invention have excellent flame retardant property；The fiber ratio
The light 20-31% of general PET fiber, changes in quality from non-porous silk at the porous fibre containing 22-30 or more air, in addition to having light and warm property
Other than energy, it is also equipped with the functions comfortable and easy to wear such as ventilative and absorbing sweat.
Embodiment 12
A kind of preparation method of modified PET polyester fiber, includes the following steps：
Modified PET polyester slice-metering-spinneret-cooling-prepared by embodiment 8 oil-is stretched-heat is fixed
Modified PET fiber is made in type-winding shaping.Wherein, the speed of winding shaping is 2600m/min, and the temperature of extrusion is 288
DEG C, cooling wind-warm syndrome is 23 DEG C；
A diameter of 15 μm through modified PET fiber made from the above method.The thermal coefficient of modified PET fiber can reach
0.04w/m.k, limit oxygen index 31.8%, modified PET fiber of the invention have excellent flame retardant property；The fiber is than one
As the light 20-31% of PET fiber, from non-porous silk change in quality at the porous fibre containing 22-30 or more air, in addition to having light and warm performance
In addition, the functions comfortable and easy to wear such as ventilative and absorbing sweat have been also equipped with.
Claims (3)
1. a kind of modified PET polyester, it is characterized in that：The modified PET polyester includes aerogel particle and poly terephthalic acid second
Diol ester, the aerogel particle are dispersed in the molecule interchain of polyethylene terephthalate；Aerogel particle exists
Content in modified PET polyester is 1-10wt%；The grain size of aerogel particle is 2-3 μm；The aerogel particle is silica aerogel
Particle；
Aerogel particles need to prepare by silica aerogel presoma, and the preparation method of silica aerogel presoma is：
（1）Prepare the mixed solution of silicon source and solvent
The sodium metasilicate for several 3.0-4.0 that rub is taken to be fitted into reaction kettle, the deionized water that 1-3 times of sodium metasilicate quality is added is diluted,
Reaction kettle is stirred 30 minutes with 80-200 revs/min of speed, through 200 mesh screens, obtains sodium silicate solution；
（2）Colloidal sol
It takes A sour, A acid metal salts is added in A acid and rare earth A hydrochlorates are added in a manner of spray to step after mixing
（1）Obtained sodium silicate solution；The material in reaction kettle is carried out quickly with 1200-2000 revs/min of speed while spray
Stirring, the pH value for controlling sodium silicate solution is 1.5-3.0, obtains colloidal sol；The A acid is sulfuric acid, hydrochloric acid, oxalic acid or nitric acid；Institute
It is A acid zirconates or A acid aluminium salts to state A acid metal salts；The rare earth A hydrochlorates are A acid cerium salt, A acid yttrium salt or A acid lanthanum salts；
（3）Gel
Sodium hydroxide or ammonium hydroxide are taken, it is 10-11.5 that deionized water, which is added, and is diluted to pH value, is added in a manner of spray to reaction kettle
In；The material in reaction kettle is quickly stirred with 1200-2000 revs/min of speed while spray, when object in reaction kettle
When the pH value of material is 4.5-5.5, spray is terminated, gel is obtained；
（4）Aging
Stirring 3-10 hours is continued with 20-50 revs/min of speed in reaction kettle, aging, control are carried out to the material in reaction kettle
Material in reactor temperature is 35-50 degrees Celsius；
（5）Solvent is replaced
It carries out continuing stirring 60-180 minutes, while addition and step in reaction kettle（4）Aging material same volume in reaction kettle
Displacement solvent, to displace remaining moisture；
（6）Surface modification
It carries out continuing stirring in reaction kettle, while continuously adding and step（4）The coupling of aging material same volume in reaction kettle
Agent；By stirring 60-180 minutes, the aerogel precursor body for being coated with displacement solvent and coupling agent is obtained.
2. modified PET polyester according to claim 1, which is characterized in that be put into the silica aerogel presoma of preparation dry
Dry kettle, in drying kettle being filled with nitrogen catches up with oxygen, until oxygen content is less than 3% in drying kettle, is then carried out to the material in drying kettle
Micro-wave vacuum；Negative pressure 0.08-0.12MPa in drying kettle, temperature 85-135°The silicon of solid powder is made in C after dry
Aerogel particle.
3. modified PET polyester according to claim 1, which is characterized in that the preparation method of modified PET polyester is：（1）It will
Silica aerogel powder is added in ethylene glycol to be placed in grinder and grind, and mixed serum, the aerosol grain size in mixed serum is made
It is 2-3 μm；（2）Esterification and polymerisation are carried out after mixed serum is mixed with terephthalic acids successively, modified polyphenyl is made
Naphthalate, i.e. modified PET.
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| CN201810482027.7A CN108409947B (en) | 2017-06-28 | 2017-06-28 | Application of modified PET polyester |
| CN201810482026.2A CN108707223A (en) | 2017-06-28 | 2017-06-28 | A kind of preparation method of modified PET polyester |
| CN201710509719.1A CN107312166B (en) | 2017-06-28 | 2017-06-28 | A kind of modified PET polyester and its preparation method and application |
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Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI732195B (en) * | 2018-05-17 | 2021-07-01 | 利機企業股份有限公司 | Flame-retardant and abrasion-resistant composite |
| CN108754630B (en) * | 2018-06-01 | 2020-10-16 | 北京弘暖纤科技有限公司 | Aerogel modified polymer fibers, wet spinning method thereof and woven fabric thereof |
| CN108715632B (en) * | 2018-06-01 | 2019-09-24 | 弘暖纤科技（北京）有限公司 | The preparation method of aeroge modified polyester fiber and aeroge modified poly ester fabric |
| CN109112665A (en) * | 2018-08-22 | 2019-01-01 | 佛山市恒新精密电器有限公司 | A kind of temperature protector suitable for wet environment |
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| CN109269204A (en) * | 2018-08-22 | 2019-01-25 | 佛山豆萁科技有限公司 | The high-low temperature chamber of high reliability |
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| CN109148239A (en) * | 2018-09-04 | 2019-01-04 | 佛山铮荣科技有限公司 | A kind of temperature protector suitable for wet environment |
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| CN109131398A (en) * | 2018-09-04 | 2019-01-04 | 佛山铮荣科技有限公司 | The rail carriages electric heater of high security |
| CN109505025A (en) * | 2018-11-27 | 2019-03-22 | 华叶莹 | A kind of anti-fire modified PET fiber and preparation method thereof |
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| CN110735194B (en) * | 2019-11-29 | 2022-07-08 | 浙江艾恋针织服饰有限公司 | Silicon dioxide composite aerogel, PET polyester fiber and polyester fabric |
| CN111286808A (en) * | 2020-04-13 | 2020-06-16 | 浙江正凯化纤有限公司 | Flame-retardant heat-resistant polyester fiber and preparation method thereof |
| CN111607838A (en) * | 2020-06-15 | 2020-09-01 | 邓颖菁 | Slow-release aromatic polyester fiber and preparation method thereof |
| CN111826737B (en) * | 2020-06-23 | 2023-03-24 | 浙江恒逸石化研究院有限公司 | Preparation method of polyamide 56 industrial yarn for safety airbag |
| CN113802269A (en) * | 2021-08-24 | 2021-12-17 | 天津朗华科技发展有限公司 | Sound-proof, fireproof and heat-insulating melt-blown fabric and preparation method and application thereof |
| CN113956448A (en) * | 2021-10-26 | 2022-01-21 | 四川东材科技集团股份有限公司 | Polyester master batch for optical film and preparation method thereof |
| CN114592246B (en) * | 2021-12-27 | 2023-01-10 | 浙江恒逸高新材料有限公司 | Preparation process of three-dimensional crimped hollow polyester staple fiber |
| CN116262990A (en) * | 2022-12-08 | 2023-06-16 | 凯泰特种纤维科技有限公司 | Light-absorbing, heating and warm-keeping polyester fiber and preparation method thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4419550B2 (en) * | 2003-12-16 | 2010-02-24 | コニカミノルタホールディングス株式会社 | Proton-conducting electrolyte membrane manufacturing method, proton-conducting electrolyte membrane, and fuel cell using proton-conducting electrolyte membrane |
| KR100567375B1 (en) * | 2004-04-22 | 2006-04-03 | 한양대학교 산학협력단 | Biodegradable aliphatic polyester/silica composite and the preparation method thereof |
| CN101481478A (en) * | 2009-02-02 | 2009-07-15 | 郑文芝 | Modified plastics with antibacterial, heat insulating, sound isolating and flame-retardant functions |
| CN102443157B (en) * | 2010-09-30 | 2013-06-05 | 中国石油化工股份有限公司 | Method for preparing aliphatic-aromatic copolyester |
| CN102674374B (en) * | 2012-04-25 | 2013-10-30 | 纳诺科技有限公司 | Preparation method of silica aerogel |
| CN103172828A (en) * | 2013-04-02 | 2013-06-26 | 江苏瑞丰科技实业有限公司 | Preparation of polyurethane wave-absorbing gel material |
| CN103388193B (en) * | 2013-08-09 | 2015-11-04 | 陕西盟创纳米新型材料股份有限公司 | The preparation method of aeroge modified synthetic fibers and obtained synthetic fiber |
| CN104941538A (en) * | 2015-06-03 | 2015-09-30 | 金承黎 | In-situ composite silicon-based multibasic oxide oxide aerogel material and preparation method thereof |
| CN104941838A (en) * | 2015-05-21 | 2015-09-30 | 池上剑 | Sprayer facilitating filtering |
| CN105802220A (en) * | 2016-04-06 | 2016-07-27 | 同济大学 | Preparation method of polyimide/silicon dioxide aerogel powder composite aerogel material |
| CN106633691A (en) * | 2016-12-01 | 2017-05-10 | 深圳中凝科技有限公司 | Aerogel PET (polyethylene terephthalate) master batch and manufacturing technique thereof |
| CN106693719B (en) * | 2016-12-02 | 2018-05-11 | 湖北硅金凝节能减排科技有限公司 | A kind of hollow-fibre membrane and preparation method thereof |
| CN106745000A (en) * | 2016-12-23 | 2017-05-31 | 伊科纳诺（北京）科技发展有限公司 | A kind of preparation method of waterglass base aerosil |
-
2017
- 2017-06-28 CN CN201810482027.7A patent/CN108409947B/en active Active
- 2017-06-28 CN CN201810482026.2A patent/CN108707223A/en active Pending
- 2017-06-28 CN CN201710509719.1A patent/CN107312166B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108409947A (en) | 2018-08-17 |
| CN107312166A (en) | 2017-11-03 |
| CN108707223A (en) | 2018-10-26 |
| CN108409947B (en) | 2021-02-12 |
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