CN104559050B - Composite material with dyeing effect as well as preparation method and application thereof - Google Patents
Composite material with dyeing effect as well as preparation method and application thereof Download PDFInfo
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- CN104559050B CN104559050B CN201510023865.4A CN201510023865A CN104559050B CN 104559050 B CN104559050 B CN 104559050B CN 201510023865 A CN201510023865 A CN 201510023865A CN 104559050 B CN104559050 B CN 104559050B
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- formaldehyde condensation
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Abstract
The invention relates to the technical field of composite materials and in particular relates to a composite material with a dyeing effect as well as a preparation method and application thereof. The composite material is directly synthesized by virtue of a method for performing in-situ synthesis on TiO2 and a nano melamino-formaldehyde condensation polymer, the nano melamino-formaldehyde condensation polymer is taken as the core, the sheet TiO2 is taken as the shell, and the composite material is of a core-shell structure. The product disclosed by the invention integrates the characteristics of two materials such as TiO2 and melamino-formaldehyde condensation polymer and has the dyeing effect of TiO2 and the flame-retardant effect of the melamino-formaldehyde condensation polymer, the application range of the TiO2 and melamino-formaldehyde condensation polymer is widened, and when TiO2 serving as an additive is added into the polymer, a dyeing effect can be achieved, and the composite material can be endowed with the flame-retardant property. The composite material is applied to household appliances parts, LED lampshades, power sockets and switches, the flame-retardant properties of the household appliances parts can be improved, the safety performance is improved, and the service life is prolonged. The preparation process is simple, and the production cost is low.
Description
Technical field
The present invention relates to technical field of composite materials is and in particular to a kind of composite with Color and its preparation
Methods and applications.
Background technology
The main component of titanium dioxide is tio2, it is widely used in the works such as coating, ink, pottery, glass as coloring pigment
In industry.As paper industry can as filler and coating material, improve paper outward appearance, can India and opacity；In rubber
Can be used as coloring agent and reinforcing agent in industry；Plastic is then filler be also coloring agent；In chemical fibre, printing and dyeing industry
For original liquid coloring and print paste etc..
Tripolycyanamide is a kind of triazines nitrogen heterocyclic ring organic compound, and nitrogen content is up to 67%, and 345 DEG C of fusing point, 350
DEG C about distillation, possess significant heat stability and anti-flammability.Tripolycyanamide can in the range of suitable temperature and acid-base value,
Methylolation and polycondensation reaction is occurred to obtain melamine resin successively with formaldehyde, it is widely used in adhesive, foam
The fields such as plastics, synthetic fibers, photoelectric material.
And current, Patents documents will not have the tio of coloration2With the nanometer trimerization with flame retardant efficiency
Cyanamide formaldehyde condensation polymer body is directly synthesized by the method for fabricated in situ.
Content of the invention
In order to overcome shortcoming and defect present in prior art, it is an object of the invention to provide one kind has dyeing effect
Composite of fruit and its preparation method and application.This composite set tio2Spy with melamino-formaldehyde bi-material
Property, have tio concurrently2Coloration and melamino-formaldehyde fire retardation, expand tio2Use model with melamino-formaldehyde
Enclose, after being added in polymer as additive, both can play the effect of dyeing, can give composite certain fire-retardant again
Performance.
The purpose of the present invention is achieved through the following technical solutions.
A kind of composite with Color, it is by tio2Pass through in situ with nano melamine formaldehyde condensation polymer body
The method of synthesis is directly synthesized, with nano melamine formaldehyde condensation polymer body as core, lamellar tio2Nucleocapsid structure composite wood for shell
Material.
Described nano melamine formaldehyde condensation polymer body refers in the acid titanium tetrachloride aqueous solution that ionization occurs, by having
Have amino in methylol (- ch2-oh) in the melamine methylol of having structure and melamine methylol molecule (-
Nh2), imino group (- nh-) or hydroxyl (- oh) occur condensation reaction to form the nanometer three with line style or branched chain type structure
Melamine-formaldehyde condensation polymer；
Described nano melamine formaldehyde condensation polymer body is a melamine methylol formaldehyde condensation polymer body, dihydroxymethyl trimerization
Cyanamide formaldehyde condensation polymer body, trihydroxy melamino-formaldehyde condensation polymer, tetra methylol melamino-formaldehyde condensation polymer, five methylols three
Melamine-formaldehyde condensation polymer, one of hexakis(hydroxymethyl)melamine formaldehyde condensation polymer body or more than one mixture；Described
Tio2 is that described tio2 exists with the nano melamine formaldehyde condensation polymer body of above-mentioned production as nucleator in titanium tetrachloride aqueous solution
Its superficial growth is formed, and has laminated structure.
A kind of preparation method of the composite with Color, comprises the following steps:
Step a: measure the formalin that mass fraction is 30-50%, deionized water adjusts ph value, makes ph be 8-9, plus
Enter certain mole of tripolycyanamide, at 65-75 DEG C, be stirred well to clarification, obtain nano melamine formaldehyde condensation polymer body standby
With the mol ratio of tripolycyanamide and formaldehyde is 1:(1-8)；
Step b: certain density titanium tetrachloride aqueous solution is placed in the there-necked flask added with condensing reflux and stirring, dimension
Hold temperature at 40-80 DEG C, stirring is fully hydrolyzed formation ionization solution；
Step c: weigh the nano melamine formaldehyde condensation polymer body that step a is obtained, instill the titanium tetrachloride of step b gained
In aqueous solution, after being added dropwise to complete whne liquid level from transparent be changed into light blue or white when, the rapid temperature that reduces to less than 30 DEG C, together
Shi Tigao speed of agitator, after temperature stabilization through filtration, deionized water wash 3 times, be drying to obtain described composite.
The volume addition of melamino-formaldehyde condensation polymer described in step c is the 8-12% of titanium tetrachloride volume.
Baking temperature described in step c is 70-100 DEG C
A kind of application process of the composite with Color it is characterised in that: will be any one in claim 3-5
A kind of composite application with Color of the preparation method preparation of the composite with Color described in
On household electrical appliances accessory, LED lamp shade, supply socket, switch, its application process includes: the composite with Color is made
It is added in the material of application product for additive and carry out blending processing
Beneficial effects of the present invention:
The composite set of gained of the present invention tio2With the characteristic of melamino-formaldehyde bi-material, have tio concurrently2's
Coloration and the fire retardation of melamino-formaldehyde, expand tio2With the range of melamino-formaldehyde, as additive
After being added in polymer, both can play the effect of dyeing, can give composite certain fire resistance again.Composite
Apply the fire resistance that household electrical appliances accessory can be increased on household electrical appliances accessory, LED lamp shade, supply socket, switch, improve safety
Energy and service life.Preparation process is simple, low production cost, worth application.
Specific embodiment
The invention will be further described with the following Examples.
Embodiment 1
A kind of composite with Color of the present embodiment, it is by tio2With nano melamine formaldehyde condensation polymer
Body is directly synthesized by the method for fabricated in situ, with nano melamine formaldehyde condensation polymer body as core, lamellar tio2Nucleocapsid for shell
Structural composite material.
Described nano melamine formaldehyde condensation polymer body refers in the acid titanium tetrachloride aqueous solution that ionization occurs, by having
Have amino in methylol (- ch2-oh) in the melamine methylol of having structure and melamine methylol molecule (-
Nh2) condensation reaction is occurred to form the nano melamine formaldehyde condensation polymer body with line style or branched chain type structure；
Described nano melamine formaldehyde condensation polymer body is a melamine methylol formaldehyde condensation polymer body, and structural formula is as follows:
A kind of preparation method of the composite with Color, comprises the following steps:
Step a: measure the formalin that mass fraction is 30%, deionized water adjusts ph value, makes ph be 8, add one
Fixed mole of tripolycyanamide, is stirred well to clarification at 65 DEG C, obtains nano melamine formaldehyde condensation polymer body standby；
Step b: certain density titanium tetrachloride aqueous solution is placed in the there-necked flask added with condensing reflux and stirring, dimension
Hold temperature at 40 DEG C, stirring is fully hydrolyzed formation ionization solution；
Step c: weigh the nano melamine formaldehyde condensation polymer body that step a is obtained, instill the titanium tetrachloride of step b gained
In aqueous solution, after being added dropwise to complete whne liquid level from transparent be changed into light blue or white when, the rapid temperature that reduces, to 25 DEG C, carries simultaneously
High speed of agitator, after temperature stabilization through filtration, deionized water wash 3 times, be drying to obtain described composite.
In described step a, the mol ratio of described tripolycyanamide and formaldehyde is 1:1.
In described step, the volume addition of melamino-formaldehyde condensation polymer described in c is the 8% of titanium tetrachloride.
In described step c, described baking temperature is 70 DEG C.
A kind of composite wood with Color of the preparation method preparation of described composite with Color
Material is applied on household electrical appliances accessory, LED lamp shade, supply socket, switch, and its application process includes: will have the compound of Color
Material is added in the material of application product as additive and carries out blending processing.
Embodiment 2
A kind of composite with Color of the present embodiment, it is by tio2With nano melamine formaldehyde condensation polymer
Body is directly synthesized by the method for fabricated in situ, with nano melamine formaldehyde condensation polymer body as core, lamellar tio2Nucleocapsid for shell
Structural composite material.
Described nano melamine formaldehyde condensation polymer body refers in the acid titanium tetrachloride aqueous solution that ionization occurs, by having
Have amino in methylol (- ch2-oh) in the melamine methylol of having structure and melamine methylol molecule (-
Nh2), imino group (- nh-) or hydroxyl (- oh) occur condensation reaction to form the nanometer three with line style or branched chain type structure
Melamine-formaldehyde condensation polymer；
Described nano melamine formaldehyde condensation polymer body is a melamine methylol formaldehyde condensation polymer body, dihydroxymethyl trimerization
The mixture that cyanamide formaldehyde condensation polymer body and trihydroxy melamino-formaldehyde condensation polymer are formed with 1:1:1, its structural formula is as follows；
A kind of preparation method of the composite with Color, comprises the following steps:
Step a: measure the formalin that mass fraction is 35%, deionized water adjusts ph value, makes ph be 8, add one
Fixed mole of tripolycyanamide, is stirred well to clarification at 67 DEG C, obtains nano melamine formaldehyde condensation polymer body standby；
Step b: certain density titanium tetrachloride aqueous solution is placed in the there-necked flask added with condensing reflux and stirring, dimension
Hold temperature at 50 DEG C, stirring is fully hydrolyzed formation ionization solution；
Step c: weigh the nano melamine formaldehyde condensation polymer body that step a is obtained, instill the titanium tetrachloride of step b gained
In aqueous solution, after being added dropwise to complete whne liquid level from transparent be changed into light blue or white when, the rapid temperature that reduces, to 25 DEG C, carries simultaneously
High speed of agitator, after temperature stabilization through filtration, deionized water wash 3 times, be drying to obtain described composite.
In described step a, the mol ratio of described tripolycyanamide and formaldehyde is 1:3.
In described step, the volume addition of melamino-formaldehyde condensation polymer described in c is the 9% of titanium tetrachloride.
In described step c, described baking temperature is 80 DEG C.
Remaining content of the present embodiment is same as Example 1, repeats no more here.
Embodiment 3
A kind of composite with Color of the present embodiment, it is by tio2With nano melamine formaldehyde condensation polymer
Body is directly synthesized by the method for fabricated in situ, with nano melamine formaldehyde condensation polymer body as core, lamellar tio2Nucleocapsid for shell
Structural composite material.
Described nano melamine formaldehyde condensation polymer body refers in the acid titanium tetrachloride aqueous solution that ionization occurs, by having
Have amino in methylol (- ch2-oh) in the melamine methylol of having structure and melamine methylol molecule (-
Nh2), imino group (- nh-) or hydroxyl (- oh) occur condensation reaction to form the nanometer three with line style or branched chain type structure
Melamine-formaldehyde condensation polymer；
Described nano melamine formaldehyde condensation polymer body is a melamine methylol formaldehyde condensation polymer body, dihydroxymethyl trimerization
Cyanamide formaldehyde condensation polymer body, trihydroxy melamino-formaldehyde condensation polymer, tetra methylol melamino-formaldehyde condensation polymer is with 1:1:1:1 group
The mixture becoming, structural formula is as follows:
A kind of preparation method of the composite with Color, comprises the following steps:
Step a: measure the formalin that mass fraction is 40%, deionized water adjusts ph value, makes ph be 8, add one
Fixed mole of tripolycyanamide, is stirred well to clarification at 70 DEG C, obtains nano melamine formaldehyde condensation polymer body standby；
Step b: certain density titanium tetrachloride aqueous solution is placed in the there-necked flask added with condensing reflux and stirring, dimension
Hold temperature at 60 DEG C, stirring is fully hydrolyzed formation ionization solution；
Step c: weigh the nano melamine formaldehyde condensation polymer body that step a is obtained, instill the titanium tetrachloride of step b gained
In aqueous solution, after being added dropwise to complete whne liquid level from transparent be changed into light blue or white when, the rapid temperature that reduces, to 27 DEG C, carries simultaneously
High speed of agitator, after temperature stabilization through filtration, deionized water wash 3 times, be drying to obtain described composite.
In described step a, the mol ratio of described tripolycyanamide and formaldehyde is 1:4.
In described step, the volume addition of melamino-formaldehyde condensation polymer described in c is the 10% of titanium tetrachloride.
In described step c, described baking temperature is 90 DEG C.
Remaining content of the present embodiment is same as Example 1, repeats no more here.
Embodiment 4
A kind of composite with Color of the present embodiment, it is by tio2With nano melamine formaldehyde condensation polymer
Body is directly synthesized by the method for fabricated in situ, with nano melamine formaldehyde condensation polymer body as core, lamellar tio2Nucleocapsid for shell
Structural composite material.
Described nano melamine formaldehyde condensation polymer body refers in the acid titanium tetrachloride aqueous solution that ionization occurs, by having
Have amino in methylol (- ch2-oh) in the melamine methylol of having structure and melamine methylol molecule (-
Nh2), imino group (- nh-) or hydroxyl (- oh) occur condensation reaction to form the nanometer three with line style or branched chain type structure
Melamine-formaldehyde condensation polymer；
Described nano melamine formaldehyde condensation polymer body is trihydroxy melamino-formaldehyde condensation polymer, tetra methylol melamine
Amine formaldehyde condensation polymer, pentamethylol melamine formaldehyde condensation polymer body, hexakis(hydroxymethyl)melamine formaldehyde condensation polymer body are with 1:1:1:1 group
The mixture becoming, its structure is as follows:
A kind of preparation method of the composite with Color, comprises the following steps:
Step a: measure the formalin that mass fraction is 45%, deionized water adjusts ph value, makes ph be 9, add one
Fixed mole of tripolycyanamide, is stirred well to clarification at 72 DEG C, obtains nano melamine formaldehyde condensation polymer body standby；
Step b: certain density titanium tetrachloride aqueous solution is placed in the there-necked flask added with condensing reflux and stirring, dimension
Hold temperature at 70 DEG C, stirring is fully hydrolyzed formation ionization solution；
Step c: weigh the nano melamine formaldehyde condensation polymer body that step a is obtained, instill the titanium tetrachloride of step b gained
In aqueous solution, after being added dropwise to complete whne liquid level from transparent be changed into light blue or white when, the rapid temperature that reduces, to 28 DEG C, carries simultaneously
High speed of agitator, after temperature stabilization through filtration, deionized water wash 3 times, be drying to obtain described composite.
In described step a, the mol ratio of described tripolycyanamide and formaldehyde is 1:6.
In described step, the volume addition of melamino-formaldehyde condensation polymer described in c is the 11% of titanium tetrachloride.
In described step c, described baking temperature is 100 DEG C.
Remaining content of the present embodiment is same as Example 1, repeats no more here.
Embodiment 5
A kind of composite with Color of the present embodiment, it is by tio2With nano melamine formaldehyde condensation polymer
Body is directly synthesized by the method for fabricated in situ, with nano melamine formaldehyde condensation polymer body as core, lamellar tio2Nucleocapsid for shell
Structural composite material.
Described nano melamine formaldehyde condensation polymer body refers in the acid titanium tetrachloride aqueous solution that ionization occurs, by having
Have amino in methylol (- ch2-oh) in the melamine methylol of having structure and melamine methylol molecule (-
nh2)、
Imino group (- nh-) or hydroxyl (- oh) occur condensation reaction formation to have line style or the nanometer of branched chain type structure
Melamino-formaldehyde condensation polymer；
Described nano melamine formaldehyde condensation polymer body is a melamine methylol formaldehyde condensation polymer body, dihydroxymethyl trimerization
Cyanamide formaldehyde condensation polymer body, trihydroxy melamino-formaldehyde condensation polymer, tetra methylol melamino-formaldehyde condensation polymer, five methylols three
The mixture that melamine-formaldehyde condensation polymer, hexakis(hydroxymethyl)melamine formaldehyde condensation polymer body are formed with 1:1:1:1:1:1, its structural formula
As follows:
A kind of preparation method of the composite with Color, comprises the following steps:
Step a: measure the formalin that mass fraction is 50%, deionized water adjusts ph value, makes ph be 9, add one
Fixed mole of tripolycyanamide, is stirred well to clarification at 75 DEG C, obtains nano melamine formaldehyde condensation polymer body standby；
Step b: certain density titanium tetrachloride aqueous solution is placed in the there-necked flask added with condensing reflux and stirring, dimension
Hold temperature at 80 DEG C, stirring is fully hydrolyzed formation ionization solution；
Step c: weigh the nano melamine formaldehyde condensation polymer body that step a is obtained, instill the titanium tetrachloride of step b gained
In aqueous solution, after being added dropwise to complete whne liquid level from transparent be changed into light blue or white when, the rapid temperature that reduces, to 28 DEG C, carries simultaneously
High speed of agitator, after temperature stabilization through filtration, deionized water wash 3 times, be drying to obtain described composite.
In described step a, the mol ratio of described tripolycyanamide and formaldehyde is 1:8.
In described step, the volume addition of melamino-formaldehyde condensation polymer described in c is the 12% of titanium tetrachloride.
In described step c, described baking temperature is 100 DEG C.
Remaining content of the present embodiment is same as Example 1, repeats no more here.
Finally it should be noted that above example is only in order to illustrating technical scheme, rather than the present invention is protected
The restriction of shield scope, although having made to explain to the present invention with reference to preferred embodiment, those of ordinary skill in the art should
Work as understanding, technical scheme can be modified or equivalent, without deviating from the reality of technical solution of the present invention
Matter and scope.
Claims (5)
1. a kind of composite with Color it is characterised in that: it is by tio2With nano melamine formaldehyde condensation polymer body
It is directly synthesized by the method for fabricated in situ, with nano melamine formaldehyde condensation polymer body as core, lamellar tio2Nucleocapsid knot for shell
Structure composite.
2. a kind of composite with Color according to claim 1 it is characterised in that: described nanometer trimerization
Cyanamide formaldehyde condensation polymer body refers in the acid titanium tetrachloride aqueous solution that ionization occurs, by the methylol trimerization with having structure
Methylol (- ch2-oh) in cyanamide and the amino (- nh2) in melamine methylol molecule, imino group (- nh-) or hydroxyl
Base (- oh) occurs condensation reaction to form the nano melamine formaldehyde condensation polymer body with line style or branched chain type structure；Described
Nano melamine formaldehyde condensation polymer body is a melamine methylol formaldehyde condensation polymer body, dihydroxymethyl melamino-formaldehyde polycondensation
Body, trihydroxy melamino-formaldehyde condensation polymer, tetra methylol melamino-formaldehyde condensation polymer, pentamethylol melamine formaldehyde contracts
Aggressiveness, one of hexakis(hydroxymethyl)melamine formaldehyde condensation polymer body or more than one mixture.
3. a kind of composite with Color according to claim 1 it is characterised in that: described tio2 is four
With the nano melamine formaldehyde condensation polymer body of above-mentioned production as nucleator in titanium chloride aqueous solution, described tio2 is in its superficial growth
Formed, there is laminated structure.
4. a kind of composite with Color according to claim 2 it is characterised in that: described have line style or
The structural formula of the nano melamine formaldehyde condensation polymer body of person's branched chain type structure is
5. a kind of application process of the composite with Color it is characterised in that: by any one in claim 1-4
A kind of described composite with Color is applied on household electrical appliances accessory, LED lamp shade, supply socket, switch, its application
Method includes: the composite with Color is added in the material of application product as additive carry out blending plus
Work.
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