CN109385234A - The synthetic method and application of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type - Google Patents
The synthetic method and application of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type Download PDFInfo
- Publication number
- CN109385234A CN109385234A CN201811066457.7A CN201811066457A CN109385234A CN 109385234 A CN109385234 A CN 109385234A CN 201811066457 A CN201811066457 A CN 201811066457A CN 109385234 A CN109385234 A CN 109385234A
- Authority
- CN
- China
- Prior art keywords
- emulsion
- adhesive
- flocking
- retardant
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C19/00—Apparatus specially adapted for applying particulate materials to surfaces
- B05C19/001—Flocking
- B05C19/002—Electrostatic flocking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic polymers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0097—Web coated with fibres, e.g. flocked
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1664—Releasability
Abstract
The invention discloses a kind of synthetic methods of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type, which is characterized in that stratum nucleare pre-emulsion, shell pre-emulsion is respectively configured；Stratum nucleare pre-emulsion and initiator solution are added drop-wise in container simultaneously, obtain seed emulsion；Then shell pre-emulsion and initiator solution are added drop-wise in seed emulsion simultaneously, charging finishes, and reaction flask is taken out after heat preservation, and by its natually cooled to room temperature, the milky emulsion of blue light is obtained after filtering；Adipic dihydrazide is added in milky emulsion, stirs, obtains uniform and stable adhesive.The method that the present invention uses in-situ polymerization, introduce new monomer and multi-component copolymer, it is prepared for the phosphorous silicone acrylic emulsion of stable storing and there is intrinsically flame retarded the third latex of silicon, so that the polyacrylate lotion itself after polymerization completely has certain anti-flammability, reduce the usage amount of blending fire retardant agent so as to improve flocking effect.
Description
Technical field
The present invention relates to the synthetic methods and application of a kind of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type, belong to spinning
It knits, Textile Chemistry and Dyeing and Finishing Engineering technical field.
Background technique
Electrostatic spinning is as a kind of Surface-micromachining process, because its product color is gorgeous, soft, cold-proof comfort, style
Uniqueness, and the technological adaptability is strong, simple process is at low cost.The industry of China's flocking in recent years is quickly grown, but still there are still
Many problems, show that product variety is single, class is not high, and added value of product is low, new varieties deficiency etc..In recent years,
The event of fire as caused by textile fabric frequently occurs, and allows it was recognized that flame-retardant modified to the progress of electrostatic spinning product
As the key subjects urgently studied.
Flocking adhesive is used as bonding textiles and villus, and the quality of performance directly affects flocking effect and product
Energy.Electrostatic adhesive is broadly divided into solvent type and emulsion type two major classes flock binder.Under conservation culture overall background, You Jirong
Agent leads to the pollution of environment seriously to limit using and developing for solvent type adhesive, thus emulsified epoxy because its safety,
Few evil becomes the trend of the times that flock binder is studied and developed.The most common a kind of adhesive of application in recent years is polyacrylic acid
Ester adhesive.Its raw material sources is extensive, is easy preparation, is cheap, easy to use, and emulsion-stabilizing, adhesion strength are excellent, glue
Film has many merits such as against weather, chemical-resistant concurrently again, is widely used in textile printing and dyeing adhesive, pigment printing, on warp thread
The numerous areas such as slurry, electrostatic spinning, waterproof coating.
Currently, acrylate adhesive is generally made using emulsion polymerization.Wherein study how to prepare core-shell structure poly-
The project for closing object is more, and nuclear-shell emulsion polymerization is that its stability of emulsion is high, bonds relative to the prime advantage of conventional emulsions
Fastness is good, anti-after tack is good, film forming and latex film dynamic performance are preferable.Meanwhile seeded emulsion polymerization can be on the boundary of core and shell
The grafting layer formed between face, increases the compatibility of two-phase, so that emulsion property be made substantially to be broken through.
As the research in relation to palyacrylate binder gradually increases and gos deep into.However, current acrylic ester adhesive
Existing deficiency seriously hinders the development of high functionality, such as: adhesive easily causes flocked fabric feel stiff, influence its at
Type and beauty；Meanwhile the adhesive of present electrostatic spinning industrial application is generally needed to solidify under 150-180 DEG C of hot conditions and be handed over
Connection, energy consumption is high；Moreover, in the actual application process, release formaldehyde gas, containing APEO, harmful to human and environment；It is produced
Product limited functionality is influenced in application aspects such as home textile, automobile interior decorations, and fire retardant functionality is poor.
In recent years, many researchers are theoretical according to in-situ polymerization, by determining the emulsifier system without APEO, construct without first
Aldehyde low-temperature self-crosslinking system, and introduce ethylene silicon class monomer and stable low temperature ring is prepared using semi-continuous seed lotion synthetic technology
The third flock binder of silicon is protected, the fire-retardant flocking adhesive of low-temperature environment-friendly is made in the form of fire retardant after blending and modifying to add.
Liu Jinshu is mixed into machine silicon monomer (D4) in acrylate co-monomers and is copolymerized, and then by crosslinking agent vinyl
Silane coupling agent is re-introduced into emulsion system in the reaction later period, finally prepares formaldehydeless low-temperature self-crosslinking type screen printing binding agent.
Xu Yixiang etc. uses vinyltriethoxysilane (AAEM) for cross-linking monomer, while introducing phosphate ester monomer, system
For a kind of styrene-acrylate emulsified liquid of low-temperature setting, the study found that the introducing of phosphate ester monomer and AAEM are remarkably improved function
Can property styrene-acrylic emulsion latex film to the adhesive force of metal base, and in metallic substrate surface form one layer of fine and close phosphating coat.
When the phosphate ester monomer of 5wt% is added in the researchs such as Inigo discovery in MMA/BA/MAA/AAEMA system, film
Salt-fog resistant time is up to 250h, has excellent adhesive force and rustless property.
Lin Ruibin etc. has synthesized ring phosphonitrile acrylate monomer, and the monomers such as itself and methyl acrylate, butyl acrylate are total to
It is poly- to prepare polymer emulsion, it is used for cotton fabric flame-proof treatment, the study found that methoxy substitution ring phosphonitrile acrylate copolymer emulsion
When for cotton fabric flame-proof treatment, after flame time 6.3s, smoldering time 0 damages the long 7cm of charcoal, has good flame retardant effect.Yin
Red equal epoxy acrylate rubber makees base-material, and emulsion copolymerization method introduces methacrylic acid dibutoxy etherophosphoric acid,
Under high conversion, it is prepared for the flame-retardant polypropelene acid esters rubber that LOI is 24%.
Zhang Taoyong etc. carries out emulsion copolymerization with allyl dimethyl phosphate and acrylate monomer, is prepared for a kind of response type
Aqueous foaming flame-retardant coatings glue arranges it to bamboo pulp fiber fabric, studies have shown that as allyl dimethyl phosphate is used
The increase of amount, the bamboo pulp fiber fabrics flame resistance significant effect after foamed flame retardant coating adhesive arranges is promoted, when allyl phosphoric acid diformazan
When the dosage of ester accounts for the 15wt% of monomer total amount, flame retardant effect is best, and the influence to other performance is small.
Phosphate is a kind of environment-friendly material, has fire-retardant, heat-resisting, anti-corrosion, good biocompatibility and improves bonding
The multifrequency natures such as performance, with excellent wettability, solubilising, emulsifying dispersivity, antistatic property and anti-flammability environmental-friendly material
Material, with the development of industry, it is industrial to be widely used in weaving, printing and dyeing, plastics, papermaking, leather and household chemicals etc.
Field.Common phosphate specifically includes that alkyl (aryl) phosphate, polyoxyethylene ether phosphate, alkylolamides phosphate, height
Molecule polyphosphate and siloxanes phosphate etc..According to the difference of phosphate ester structure, application field also difference.
Upper research discovery accordingly: there is researcher that organic silicon monomer is grafted in acrylic ester adhesive, then add fire-retardant
Agent blending and modifying obtains the third adhesive of silicon of anti-flammability；Also there is researcher that phosphoric acid ester monomer is grafted to acrylic ester adhesive
In, then add Nano-meter SiO_22It is blended and obtains soft modified phosphoric acrylic ester adhesive.
Currently, having in-situ polymerization and mechanical blending to the method for modifying of palyacrylate binder flame retardant property.But it is logical
The bad and a large amount of fire retardant of its flame retardant effect of adhesive for crossing that mechanical blending mode obtains, which is blended on flocked fabric, to be caused
Fabric feeling hardens and flocking fastness is deteriorated.In recent years, it since people's lives quality is higher and higher, allows it was recognized that right
Product carries out the flame-retardant modified key subjects for having become and urgently studying.
Summary of the invention
The technical problems to be solved by the present invention are: how to improve the flame retardant effect of adhesive.
To solve the above-mentioned problems, the present invention provides a kind of conjunctions of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type
At method, which comprises the following steps:
Step 1): respectively by emulsifier used in stratum nucleare, shell, deionized water and monomer used, including methacrylic acid
Methyl esters (MMA), ethyl acrylate (EA) and n-butyl acrylate (BA) are added in container A, ultrasonic under room temperature, are then heated to
30~35 DEG C, stirring makes it be uniformly dispersed, and respectively obtains stratum nucleare pre-emulsion, shell pre-emulsion；
Step 2): being warming up to 78~80 DEG C for container B, is then added drop-wise to stratum nucleare pre-emulsion simultaneously with initiator solution
In container B, when reaction system has obvious blue light, accelerate rate of addition, charging finishes, and is warming up to 85 DEG C, and heat preservation obtains seed
Lotion；
Step 3): being cooled to 78~80 DEG C for seed emulsion, then drips shell pre-emulsion simultaneously with initiator solution
It is added in seed emulsion, charging finishes, and reaction flask is taken out after heat preservation, by its natually cooled to room temperature, obtains indigo plant after filtering
The milky emulsion of light；
Step 4): with n Diacetone Acrylamide (DAAM)/n adipic dihydrazide (ADH)=1:1 in milky emulsion
Molar ratio be added adipic dihydrazide (ADH), stirring, obtain uniform and stable adhesive.
Preferably, the ultrasonic time in the step 1) is 15min；The revolving speed of stirring is 500-600r/min, when stirring
Between be 45min.
Preferably, the step 2), the mass concentration of initiator solution is 0.4% in step 3).
Preferably, the mass ratio of the initiator in the step 2) in initiator solution and stratum nucleare pre-emulsion is 1:841.
Preferably, the reaction system in the step 2) is kept stirring, and stirring rate is 300~350r/min；When heat preservation
Between be 2h.
Preferably, the mass ratio of the initiator in the step 3) in initiator solution and shell pre-emulsion is 1:464.
Preferably, the mixing time in the step 4) is 15min.
The present invention also provides a kind of synthetic methods of above-mentioned fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type to obtain
Adhesive application, which is characterized in that adhesive is evenly applied to all-cotton fabric surface with coating machine, villus is got out and sets
In the corresponding position of flocking machine, opens flocking machine and carry out flocking.
Preferably, described adhesive is adjusted to appropriate viscosity through ammonium hydroxide in advance using preceding.
Preferably, the technological parameter of the flocking machine are as follows: flocking 10~20cm of pole span, 3~3.5kV/cm of electric field strength plant
The suede time is 5s.
The method that the present invention uses in-situ polymerization replaces original functional and grafted-organosilicon monomer with pam-100,
New monomer and multi-component copolymer are introduced, the phosphorous silicone acrylic emulsion of stable storing is prepared for and there is intrinsically flame retarded silicon third
Latex reduces making for blending fire retardant agent so that the polyacrylate lotion itself after polymerization completely has certain anti-flammability
Dosage is so as to improve flocking effect；The flocked fabric of preparation has the function of fire-retardant simultaneously, and flexibility and wearability are preferable.
Specific embodiment
In order to make the present invention more obvious and understandable, it is hereby described in detail below with preferred embodiment.
It is as follows that product made from embodiment 1-4 carries out correlated performance test:
1, flame retardant property testing standard: GBT 5455-2014.
2, flocking fastness testing standard: GB/T 13775.
3, feel is tested: with one group of 5~10 people, being touched, is graded to finish fabric.Feel is divided into 5 grades, with
Unfinished blank cloth is set to 1 grade, feel it is best be set to 5 grades.
4, colorfastness to rubbing testing standard: GB/T 29865-2013 (the round friction head of facet area method).
5, tension failure strength test standard: GB/T 3923.1-2013.
6, fabric bursting strength testing standard: GB/T 19976-2005.
7, bending length testing standard: GB/T 7689.4-2013 (is measured) using inclined plane method.
8, scanning electron microscope (SEM): using the TM-1000 type instrument of Hitachi company, Japan.
Embodiment 1
Step 1: the preparation of adhesive
The preparation of core-shell emulsion: by stratum nucleare emulsifier fatty alcohol polyoxyethylene ether (AEO-9), deionized water and methyl-prop
E pioic acid methyl ester (MMA), ethyl acrylate (EA) and n-butyl acrylate (BA) are added in the four-hole boiling flask of 500mL, at 55 DEG C
Ultrasonic 15min then heats to 58 DEG C, stirs 45min under 580r/min revolving speed, it is made to be uniformly dispersed, and obtains the pre- cream of stratum nucleare
Change liquid；By shell emulsifier (AEO-9), deionized water and methyl methacrylate (MMA), ethyl acrylate (EA) and propylene
Sour N-butyl (BA) is added in the four-hole boiling flask of 500mL, and ultrasound 15min, then heats to 58 DEG C, in 580r/min at 55 DEG C
45min is stirred under revolving speed, it is made to be uniformly dispersed, obtains shell pre-emulsion.
0.4g ammonium persulfate (APS) is added in 10mL water and configures initiator solution, separates 5mL and syringe pump is added, by core
Layer pre-emulsion is added in dropping funel and (reserves about 1/4 in former flask).
Be warming up to 82 DEG C, while ammonium persulfate (APS) solution and stratum nucleare pre-emulsion be added dropwise, when polymerization reaction system have it is bright
Appropriate to accelerate monomer dropping speed when aobvious blue light, time for adding about 2h (controls temperature and is no more than 88 DEG C), fed during charging
Finish, be warming up to 90 DEG C, stirring rate is maintained at 330r/min, keeps the temperature 2h up to seed emulsion.
The seed emulsion of preparation is cooled to 80 DEG C, while shell pre-emulsion and 5mL initiator is added dropwise.Take out reaction
Bottle, natually cooled to room temperature obtain the milky emulsion of blue light with 200 mesh nylon net cloth filtering and dischargings；2g ADH is added,
Stir about 15min obtains uniform and stable adhesive.
Step 2: electrostatic spinning
Adhesive suitably adjusts viscosity through ammonium hydroxide before flocking, is then evenly applied to fabric surface, and flocking pole span is
15cm, electric field strength 3.5kV/cm, flocking time are 5s.
Embodiment 2
Step 1: the preparation of adhesive
The preparation of core-shell emulsion: by stratum nucleare emulsifier fatty alcohol polyoxyethylene ether (AEO-9), deionized water and methyl-prop
E pioic acid methyl ester (MMA), ethyl acrylate (EA) and n-butyl acrylate (BA) are added in the four-hole boiling flask of 500mL, at 55 DEG C
Ultrasonic 15min then heats to 58 DEG C, stirs 45min under 580r/min revolving speed, it is made to be uniformly dispersed, and obtains the pre- cream of stratum nucleare
Change liquid；By shell emulsifier (AEO-9), deionized water and methyl methacrylate (MMA), ethyl acrylate (EA) and propylene
Sour N-butyl (BA) is added in the four-hole boiling flask of 500mL, and ultrasound 15min, then heats to 58 DEG C, in 580r/min at 55 DEG C
45min is stirred under revolving speed, it is made to be uniformly dispersed, obtains shell pre-emulsion.
0.4g ammonium persulfate (APS) is added in 10mL water and configures initiator solution, separates 5mL and syringe pump is added, by core
Layer pre-emulsion is added in dropping funel and (reserves about 1/4 in former flask).
Be warming up to 84 DEG C, while ammonium persulfate (APS) solution and stratum nucleare pre-emulsion be added dropwise, when polymerization reaction system have it is bright
Appropriate to accelerate monomer dropping speed when aobvious blue light, time for adding about 2h (controls temperature and is no more than 88 DEG C), fed during charging
Finish, be warming up to 90 DEG C, stirring rate is maintained at 330r/min, keeps the temperature 2h up to seed emulsion.
The seed emulsion of preparation is cooled to 80 DEG C, while shell pre-emulsion and 5mL initiator is added dropwise.Take out reaction
Bottle, natually cooled to room temperature obtain the milky emulsion of blue light with 200 mesh nylon net cloth filtering and dischargings；2g ADH is added,
Stir about 15min obtains uniform and stable adhesive.
Step 2: electrostatic spinning
Adhesive suitably adjusts viscosity through ammonium hydroxide before flocking, is then evenly applied to fabric surface, and flocking pole span is
15cm, electric field strength 3.5kV/cm, flocking time are 5s.
Embodiment 3
Step 1: the preparation of adhesive
The preparation of core-shell emulsion: by stratum nucleare emulsifier fatty alcohol polyoxyethylene ether (AEO-9), deionized water and methyl-prop
E pioic acid methyl ester (MMA), ethyl acrylate (EA) and n-butyl acrylate (BA) are added in the four-hole boiling flask of 500mL, at 55 DEG C
Ultrasonic 15min then heats to 58 DEG C, stirs 45min under 580r/min revolving speed, it is made to be uniformly dispersed, and obtains the pre- cream of stratum nucleare
Change liquid；By shell emulsifier (AEO-9), deionized water and methyl methacrylate (MMA), ethyl acrylate (EA) and propylene
Sour N-butyl (BA) is added in the four-hole boiling flask of 500mL, and ultrasound 15min, then heats to 58 DEG C, in 580r/min at 55 DEG C
45min is stirred under revolving speed, it is made to be uniformly dispersed, obtains shell pre-emulsion.
0.4g ammonium persulfate (APS) is added in 10mL water and configures initiator solution, separates 5mL and syringe pump is added, by core
Layer pre-emulsion is added in dropping funel and (reserves about 1/4 in former flask).
Be warming up to 86 DEG C, while ammonium persulfate (APS) solution and stratum nucleare pre-emulsion be added dropwise, when polymerization reaction system have it is bright
Appropriate to accelerate monomer dropping speed when aobvious blue light, time for adding about 2h (controls temperature and is no more than 88 DEG C), fed during charging
Finish, be warming up to 90 DEG C, stirring rate is maintained at 330r/min, keeps the temperature 2h up to seed emulsion.
The seed emulsion of preparation is cooled to 80 DEG C, while shell pre-emulsion and 5mL initiator is added dropwise.Take out reaction
Bottle, natually cooled to room temperature obtain the milky emulsion of blue light with 200 mesh nylon net cloth filtering and dischargings；2g ADH is added,
Stir about 15min obtains uniform and stable adhesive.
Step 2: electrostatic spinning
Adhesive suitably adjusts viscosity through ammonium hydroxide before flocking, is then evenly applied to fabric surface, and flocking pole span is
15cm, electric field strength 3.5kV/cm, flocking time are 5s.
Embodiment 4
Step 1: the preparation of adhesive
The preparation of core-shell emulsion: by stratum nucleare emulsifier fatty alcohol polyoxyethylene ether (AEO-9), deionized water and methyl-prop
E pioic acid methyl ester (MMA), ethyl acrylate (EA) and n-butyl acrylate (BA) are added in the four-hole boiling flask of 500mL, at 55 DEG C
Ultrasonic 15min then heats to 58 DEG C, stirs 45min under 580r/min revolving speed, it is made to be uniformly dispersed, and obtains the pre- cream of stratum nucleare
Change liquid；By shell emulsifier (AEO-9), deionized water and methyl methacrylate (MMA), ethyl acrylate (EA) and propylene
Sour N-butyl (BA) is added in the four-hole boiling flask of 500mL, and ultrasound 15min, then heats to 58 DEG C, in 580r/min at 55 DEG C
45min is stirred under revolving speed, it is made to be uniformly dispersed, obtains shell pre-emulsion.
0.4g ammonium persulfate (APS) is added in 10mL water and configures initiator solution, separates 5mL and syringe pump is added, by core
Layer pre-emulsion is added in dropping funel and (reserves about 1/4 in former flask).
Be warming up to 88 DEG C, while ammonium persulfate (APS) solution and stratum nucleare pre-emulsion be added dropwise, when polymerization reaction system have it is bright
Appropriate to accelerate monomer dropping speed when aobvious blue light, time for adding about 2h (controls temperature and is no more than 88 DEG C), fed during charging
Finish, be warming up to 90 DEG C, stirring rate is maintained at 330r/min, keeps the temperature 2h up to seed emulsion.
The seed emulsion of preparation is cooled to 80 DEG C, while shell pre-emulsion and 5mL initiator is added dropwise.Take out reaction
Bottle, natually cooled to room temperature obtain the milky emulsion of blue light with 200 mesh nylon net cloth filtering and dischargings；2g ADH is added,
Stir about 15min obtains uniform and stable adhesive.
Step 2: electrostatic spinning
Adhesive suitably adjusts viscosity through ammonium hydroxide before flocking, is then evenly applied to fabric surface, and flocking pole span is
15cm, electric field strength 3.5kV/cm, flocking time are 5s.
Test result is as follows for product made from embodiment 1-4:
1. feel is tested: with one group of 5~10 people, touching, grade to finish fabric.Feel is divided into 5 grades, with
Unfinished blank cloth is set to 1 grade, feel it is best be set to 5 grades.
2. flame retardant property is tested: according to the anti-flammability of GBT 5455-2014 standard testing fabric.
3. flocking fastness is tested: the third flock binder of flame retardant type silicon that the present invention synthesizes both has certain flame retardant effect,
Higher flocking fastness can be ensured again, while obtaining relatively soft feel, solved to assign while the relationship of feel and fastness and be planted
The certain anti-flammability of suede product.Adhesive spread 250g/m is probed into test2, 120 DEG C of baking temperature, time 4min is baked, i.e.,
It can reach higher flocking fastness >=9900 time, bending length is only 1.73cm, soft, 3-4 grades reachable, dry fastness
It can reach 4-5 grades, fastness to wet rubbing can reach 4 grades, and indices reach the standard that electrostatic spinning takes product Grade A.
Claims (10)
1. a kind of synthetic method of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type, which comprises the following steps:
Step 1): respectively by emulsifier used in stratum nucleare, shell, deionized water and monomer used, including methyl methacrylate,
Ethyl acrylate and n-butyl acrylate are added in container A, ultrasonic under room temperature, then heat to 30~35 DEG C, stirring makes it
It is uniformly dispersed, respectively obtains stratum nucleare pre-emulsion, shell pre-emulsion；
Step 2): being warming up to 78~80 DEG C for container B, and stratum nucleare pre-emulsion and initiator solution are then added drop-wise to container simultaneously
In B, when reaction system has obvious blue light, accelerate rate of addition, charging finishes, and is warming up to 85 DEG C, and heat preservation obtains seed cream
Liquid；
Step 3): being cooled to 78~80 DEG C for seed emulsion, is then added drop-wise to shell pre-emulsion simultaneously with initiator solution
In seed emulsion, charging is finished, and reaction flask is taken out after heat preservation, by its natually cooled to room temperature, obtains blue light after filtering
Milky emulsion；
Step 4): oneself is added two with n Diacetone Acrylamide/n adipic dihydrazide=1:1 molar ratio in milky emulsion
Acid dihydrazide, stirring, obtains uniform and stable adhesive.
2. the synthetic method of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type as described in claim 1, which is characterized in that
Ultrasonic time in the step 1) is 15min；The revolving speed of stirring is 500-600r/min, mixing time 45min.
3. the synthetic method of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type as described in claim 1, which is characterized in that
The mass concentration of initiator solution is 0.4% in the step 2), step 3).
4. the synthetic method of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type as described in claim 1, which is characterized in that
The mass ratio of initiator and stratum nucleare pre-emulsion in the step 2) in initiator solution is 1:841.
5. the synthetic method of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type as described in claim 1, which is characterized in that
Reaction system in the step 2) is kept stirring, and stirring rate is 300~350r/min；Soaking time is 2h.
6. the synthetic method of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type as described in claim 1, which is characterized in that
The mass ratio of initiator and shell pre-emulsion in the step 3) in initiator solution is 1:464.
7. the synthetic method of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type as described in claim 1, which is characterized in that
Mixing time in the step 4) is 15min.
8. a kind of synthetic method of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type described in claim 1-7 any one
The application of obtained adhesive, which is characterized in that adhesive is evenly applied to all-cotton fabric surface with coating machine, gets out suede
Hair is placed in the corresponding position of flocking machine, opens flocking machine and carries out flocking.
9. the application of adhesive as claimed in claim 8, which is characterized in that described adhesive is adjusted through ammonium hydroxide in advance using preceding
To appropriate viscosity.
10. the application of adhesive as claimed in claim 8, which is characterized in that the technological parameter of the flocking machine are as follows: flocking pole
Away from 10~20cm, 3~3.5kV/cm of electric field strength, the flocking time is 5s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811066457.7A CN109385234A (en) | 2018-09-13 | 2018-09-13 | The synthetic method and application of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811066457.7A CN109385234A (en) | 2018-09-13 | 2018-09-13 | The synthetic method and application of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109385234A true CN109385234A (en) | 2019-02-26 |
Family
ID=65418947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811066457.7A Pending CN109385234A (en) | 2018-09-13 | 2018-09-13 | The synthetic method and application of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109385234A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100026472A (en) * | 2008-08-29 | 2010-03-10 | 한국화학연구원 | Acrylic adhesives with water-resistance |
| CN102321326A (en) * | 2011-06-29 | 2012-01-18 | 三棵树涂料股份有限公司 | Acrylic ester elastic emulsion of room-temperature self crosslinking nucleocapsid structure and preparation method thereof |
-
2018
- 2018-09-13 CN CN201811066457.7A patent/CN109385234A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100026472A (en) * | 2008-08-29 | 2010-03-10 | 한국화학연구원 | Acrylic adhesives with water-resistance |
| CN102321326A (en) * | 2011-06-29 | 2012-01-18 | 三棵树涂料股份有限公司 | Acrylic ester elastic emulsion of room-temperature self crosslinking nucleocapsid structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴海婷等: "低温无甲醛硅丙静电植绒粘合剂LF的合成与应用", 《印染助剂》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105294925B (en) | Electrostatic flocking adhesive for high fastness carpet and preparation method thereof | |
| CN102199239B (en) | Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure | |
| US3203919A (en) | Acrylic/siloxane copolymer, polysiloxane composition containing same, and article coated with the composition | |
| CN104831540A (en) | Water-repellent, oil-repellent, sun-proof, anti-bend torsion and cold-resistant matt-leather-membrane aqueous coating adhesive for textiles and preparation method of matt-leather-membrane aqueous coating adhesive | |
| CN106496451A (en) | A kind of imitative reactive coating printing adhesive copolymer and preparation method thereof | |
| CN104119483B (en) | A kind of preparation method of modified acrylate emulsion | |
| CN105111363B (en) | A kind of function performed polymer and preparation method and application | |
| US20020035186A1 (en) | Diorganopolysiloxane/acrylate ester copolymer emulsion composition for fabric treatment | |
| CN103193917A (en) | Method for preparing pure acrylate copolymer coating emulsion for building external wall elastic coating | |
| CN109400793A (en) | A kind of hydrophobically modified acrylic acid ester emulsion and preparation method thereof | |
| CN109680522A (en) | A kind of research of silicone modified coating printing paste used for textiles and preparation method | |
| CN104419359A (en) | Flocking adhesive as well as preparation method thereof | |
| CN101768880A (en) | Pearl powder printing paste composition, preparing method thereof and application thereof | |
| CN105885740A (en) | Cationic binder for denim paint dyeing | |
| CN105602494A (en) | Organosilicone modified waterborne acrylate electrostatic flocking formaldehyde-free adhesive and preparation method thereof | |
| CN107476063B (en) | The good water-and acrylate coating adhesive used for textiles and preparation method thereof of soft, cold-resistant, elastic, fastness, resistance to hydrostatic pressure performance | |
| CN109385234A (en) | The synthetic method and application of fire-retardant the third flocking adhesive of silicon of low-temperature environment-friendly type | |
| CN1208359C (en) | Modified polyacrylate microemulsion, synthesis mehtod and use thereof | |
| CN114044861A (en) | Polyurethane modified acrylate pigment printing adhesive for dacron oxford fabric and preparation method thereof | |
| CN104411880B (en) | Moisture-permeable water-proof fabric | |
| CN109629263B (en) | Active-like adhesive composition and preparation method thereof | |
| CN102108110A (en) | Method for preparing acrylate printing adhesive | |
| CN111072520A (en) | Modified curcumin with carbon-carbon double bond, prepared environment-friendly fluorescent water-based acrylic resin and preparation method | |
| CN103183774A (en) | Method for preparing seed emulsion | |
| CN115262241A (en) | Surface treatment method of textile, special hyperchromic repairing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190226 |