CN109810622A - The preparation method of normal temperature solidifying water polyurethane/boron nitride nanometer composite coating and its film - Google Patents
The preparation method of normal temperature solidifying water polyurethane/boron nitride nanometer composite coating and its film Download PDFInfo
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- CN109810622A CN109810622A CN201910012878.XA CN201910012878A CN109810622A CN 109810622 A CN109810622 A CN 109810622A CN 201910012878 A CN201910012878 A CN 201910012878A CN 109810622 A CN109810622 A CN 109810622A
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- boron nitride
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Abstract
The present invention relates to chemical technology fields, the preparation method of a kind of normal temperature solidifying water polyurethane/boron nitride nanometer composite coating and its film is disclosed, which is grouped as by the group of following weight ratio: aqueous polyurethane: nm-class boron nitride: low boiling point solvent=60~98:2 ~ 40:25 ~ 2500.Nm-class boron nitride can be made to obtain in a solvent by ultrasonic disperse and mechanical stirring in the present invention evenly dispersed, there is amino (- NH with rear surface2) or hydroxyl (- OH) nm-class boron nitride as crosslinking agent, can directly crosslink and react at normal temperature with isocyano (- NCO), formed inierpeneirating network structure, thus make preparation composite coating thermal stability, mechanical property and water resistance be remarkably reinforced.The thermodynamic property and water resistance of coating of the invention are higher, preparation process can ambient operation, simple and easy, raw material is easy to get and cost is relatively low, be suitable for industrialized production.
Description
Technical field
It is the present invention relates to chemical technology field, in particular to a kind of using nm-class boron nitride as the aqueous poly- ammonia of addO-on therapy
The preparation method of ester/boron nitride nanometer composite coating and its film.
Background technique
Aqueous polyurethane using water as decentralized medium, by the high rigidity of polyurethane coating film, strong adhesive force, easily film forming the advantages that with
The low VOC performance of water-based emulsion combines, and is widely used in the every field of national economy, such as coating, adhesive, synthetic leather
Etc. industries.However, due to the introducing of hydrophilic group, lack strong chemical crosslinking in film forming, aqueous polyurethane film it is water-fast
Property, solvent resistance, thermodynamic property and antiseptic property are all poor, it is therefore desirable to be modified to it.Traditional method of modifying are as follows: (1)
Change the structure of aqueous polyurethane；(2) it is modified using nano material.But the former preparation process is complex, cost
It is higher；The latter needs to be modified nano material, and high temperature is wanted to form a film, and limits the development of aqueous polyurethane.Therefore, it sends out
The excellent aqueous polyurethane coating method of a kind of bright simple process, normal temperature cure processability is particularly important.
Summary of the invention
Goal of the invention: aiming at the problems existing in the prior art, the present invention provides a kind of normal temperature solidifying water polyurethane/nitrogen
Change the preparation method of boron nano composite dope and its film, the thermodynamic property and water resistance of the coating are higher, preparation process
Can ambient operation, simple and easy, raw material is easy to get and cost is relatively low, be suitable for industrialized production.
Technical solution: the present invention provides a kind of normal temperature solidifying water polyurethane/boron nitride nanometer composite coatings, by following
The group of weight ratio is grouped as: aqueous polyurethane: nm-class boron nitride: low boiling point solvent=60~98:2 ~ 40:25 ~ 2500.
Preferably, the nm-class boron nitride is the nm-class boron nitride that surface has amino or hydroxyl.
Preferably, the aqueous polyurethane is the aqueous polyurethane of isocyano sealing end.Aqueous polyurethane be for ink,
The aqueous polyurethane of leather coating and adhesive industry.
Preferably, the low boiling point solvent is ketone miscible with water, ethers or esters, and boiling point is lower than 80 DEG C.
Preferably, the nm-class boron nitride is h-BN type.Commercially available nano-hexagonal boron nitride (h-BN) is due to high
Specific surface energy has remaining amino (- NH during preparation process and storage2) or hydroxyl (- OH), therefore can and isocyanic acid
The aqueous polyurethane of root (- NCO) sealing end reacts at normal temperature, forms inierpeneirating network structure, enhances the degree of cross linking, to improve
The thermodynamic property and water resistance of aqueous polyurethane.
Preferably, the partial size of the nm-class boron nitride is 10~500nm.
The present invention also provides the preparations of a kind of normal temperature solidifying water polyurethane/boron nitride nanometer composite coating and its film
Method, comprising the following steps: S1: there is the nm-class boron nitride of amino or hydroxyl to be added in low boiling point solvent surface, ultrasound
Dispersion, obtains dispersion liquid；S2: being added the aqueous polyurethane of isocyano sealing end in the dispersion liquid, and high-speed stirred obtains aqueous poly-
Urethane/boron nitride nanometer composite coating；S3: by the aqueous polyurethane/boron nitride nanometer composite coating plastic film mulch, room temperature curing is obtained
Aqueous polyurethane/boron nitride nanometer compelx coating.
Preferably, in the S1, the time of ultrasonic disperse is 20~60 min.
Preferably, in the S2, the time of high-speed stirred is 30~60 min, and revolving speed is 500~2000 rpm.
Further, in the S3, the aqueous polyurethane/boron nitride nanometer composite coating is laid on substrate,
The aqueous polyurethane/boron nitride nanometer compelx coating is obtained after room temperature curing 1~3 day.
The utility model has the advantages that the present invention has chosen " white graphite " boron nitride nanosheet lower compared with graphene price as function
Change is filled with agent, makes coating cost performance with higher.Nm-class boron nitride structure is similar to graphene, have " white graphite " it
Claim, is widely used in chemical industry, textile industry, aerospace flight technology and other sophisticated industry departments.Compared with graphene, nitrogen
Changing boron has excellent thermal stability, thermal conductivity, electrical insulating property, inoxidizability and chemical stability, is used to change by researcher
The performances such as the thermal conductivity of kind polymer coating and rub resistance.
The dispersibility of nano material in the base has extreme influence to the performance of composite coating, therefore the present invention passes through ultrasound
Dispersion keeps nm-class boron nitride evenly dispersed in a solvent, is then dispersed in aqueous polyurethane by high-speed stirred.
Solvent in the component of composite coating of the invention selects low boiling point solvent, so that this composite coating is on substrate upper berth
Can solidify to obtain compelx coating at room temperature after film, with needed after plastic film mulch using the coating of other solvents in the prior art plus
Heat cure is compared, and the present invention can be suitable for the large objects such as the film, such as ship on large object surface, and inconvenience adds after film
Heat, and use this coating then can film-forming at room temperature, greatly expand the scope of application of this composite coating.
Paint preparation technology of the invention can ambient operation, simple and easy, raw material is easy to get and cost is relatively low, be suitable for industry
Metaplasia produces.
Detailed description of the invention
Fig. 1 is the SEM photograph of nm-class boron nitride；
Fig. 2 is the infared spectrum of nm-class boron nitride；
Fig. 3 is strain-stress curve of the aqueous polyurethane nano composite material of compound different content boron nitride.
Specific embodiment
The present invention is described in detail With reference to embodiment.
Embodiment 1:
Its SEM photograph of 3.5 g(of nm-class boron nitride and infared spectrum are weighed respectively such as Fig. 1 and 2), are added in 15ml acetone, ultrasound
Disperse 20 min and obtains dispersion liquid；The aqueous polyurethane (F0407) that 100 g solid contents are 35%, 1000 rpm are added in dispersion liquid
30 min are stirred, aqueous polyurethane/boron nitride nanometer composite coating is obtained；The above-mentioned composite coating of 40 g is taken to be laid in PP box,
Normal temperature cure 3 days, obtain aqueous polyurethane/boron nitride nanometer compelx coating that mass fraction is 10 wt%.
Film performance test method: mechanical property is tested at 25 DEG C with microcomputer controlled electronic universal testing machine.Batten ruler
Very little is 65 mm*25 mm, and thickness is measured using micrometer caliper, and tensile speed is 200 mm/min；Test out tensile strength
For 14.57 MPa, elongation at break 642%.
Thermal weight loss DTG-60H(SHIMAPZU) type Instrument measurement, in air atmosphere, heating rate be 20 DEG C/
Min, sampling amount are about 5 mg；Testing out maximum decomposition temperature is 413 DEG C, and the residual volume of 700 DEG C of samples is 5.75%.
Water resistance test is after sample to be cut into appropriately sized and weighing, to be soaked into deionized water, at regular intervals
It is drawn off and quickly wipes dry weighing until constant weight, water absorption rate calculate according to the following formula: q=(m1-m2)/m2×100%,
Wherein q is water absorption rate (%), m1For the sample quality (g) after water suction, m2For the sample quality (g) before water suction；Test out suction
Water rate is 18.7%.
Embodiment 2:
7.0 g of nm-class boron nitride is weighed, is added in 30 ml acetone, 20 min of ultrasonic disperse obtains dispersion liquid；It is added in dispersion liquid
The aqueous polyurethane (F0407) that 100 g solid contents are 35%, 1000 rpm stir 30 min, obtain aqueous polyurethane/boron nitride
Nano composite dope；The above-mentioned composite coating of 40 g is taken to be laid in PP box, normal temperature cure 3 days, obtaining mass fraction was 20 wt%
Aqueous polyurethane/boron nitride nanometer compelx coating.
Film performance test method is identical with embodiment 1, herein than repeating.Test result are as follows: tensile strength
For 19.57 MPa, elongation at break 612%；Maximum decomposition temperature is 426 DEG C, and the residual volume of 700 DEG C of samples is 11.52%；
Water absorption rate is 17.5%.
Embodiment 3:
10.5 g of nm-class boron nitride is weighed, is added in 50 ml acetone, 20 min of ultrasonic disperse obtains dispersion liquid；Add in dispersion liquid
Enter the aqueous polyurethane (F0407) that 100 g solid contents are 35%, 1000 rpm stir 30 min, obtain aqueous polyurethane/nitridation
Boron nano composite dope；The above-mentioned composite coating of 40 g is taken to be laid in PP box, normal temperature cure 3 days, obtaining mass fraction was 30
The aqueous polyurethane of wt%/boron nitride nanometer compelx coating.
Film performance test method is identical with embodiment 1, herein than repeating.Test result are as follows: tensile strength
For 27.35 MPa, elongation at break is 675 %；Maximum decomposition temperature is 445 DEG C, and the residual volume of 700 DEG C of samples is 20.92%；
Water absorption rate is 8.1%.
Embodiment 4:
14.0 g of nm-class boron nitride is weighed, is added in 150 ml acetone, 20 min of ultrasonic disperse obtains dispersion liquid；Add in dispersion liquid
Enter the aqueous polyurethane (F0407) that 100 g solid contents are 35%, 1000 rpm stir 30 min, obtain aqueous polyurethane/nitridation
Boron nano composite dope；The above-mentioned composite coating of 40 g is taken to be laid in PP box, normal temperature cure 3 days, obtaining mass fraction was 40
Wt% aqueous polyurethane/boron nitride nanometer compelx coating.
Film performance test method is identical with embodiment 1, herein than repeating.Test result are as follows: tensile strength
For 14.10 MPa, elongation at break 393%；Maximum decomposition temperature is 453 DEG C, and the residual volume of 700 DEG C of samples is 26.34%；It inhales
Water rate is 5.0%.
Comparative example:
Taking solid content is that 35% 40 g of aqueous polyurethane (F0407) is laid in PP box, and normal temperature cure 3 days, it is poly- to obtain water-based
Urethane coating.
Coating performance test method is identical with embodiment 1, herein than repeating.Test result are as follows: tensile strength
For 4.16 MPa, elongation at break 384%；Maximum decomposition temperature is 398 DEG C, and 700 DEG C of samples are without remnants；Water absorption rate is
27.3%。
As shown in Figure 3 it is found that above embodiment 1 ~ 4 is compared with comparative example, when additive amount is 10~40 wt%, by
In the addition of nm-class boron nitride, mechanical property, thermal stability and the water resistance of aqueous polyurethane coating are obtained significantly
It is promoted.
The technical concepts and features of above embodiment only to illustrate the invention, its object is to allow be familiar with technique
People cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent transformation or modification that Spirit Essence is done, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of normal temperature solidifying water polyurethane/boron nitride nanometer composite coating, it is characterised in that: by the component of following weight ratio
Composition: aqueous polyurethane: nm-class boron nitride: low boiling point solvent=60~98:2 ~ 40:25 ~ 2500.
2. normal temperature solidifying water polyurethane/boron nitride nanometer composite coating according to claim 1, it is characterised in that: institute
Stating nm-class boron nitride is the nm-class boron nitride that surface has amino or hydroxyl.
3. normal temperature solidifying water polyurethane/boron nitride nanometer composite coating according to claim 1, it is characterised in that: institute
State the aqueous polyurethane that aqueous polyurethane is isocyano sealing end.
4. normal temperature solidifying water polyurethane/boron nitride nanometer composite coating according to any one of claim 1 to 3,
Be characterized in that: the low boiling point solvent is ketone miscible with water, ethers or esters, and boiling point is lower than 80 DEG C.
5. normal temperature solidifying water polyurethane/boron nitride nanometer composite coating according to any one of claim 1 to 3,
Be characterized in that: the nm-class boron nitride is h-BN type.
6. normal temperature solidifying water polyurethane/boron nitride nanometer composite coating according to any one of claim 1 to 3,
Be characterized in that: the partial size of the nm-class boron nitride is 10~500 nm.
7. a kind of normal temperature solidifying water polyurethane/boron nitride nanometer composite coating as described in any one of claim 1 ~ 6 and
The preparation method of its film, which comprises the following steps:
S1: there is the nm-class boron nitride of amino or hydroxyl to be added in low boiling point solvent surface, ultrasonic disperse obtains dispersion liquid；
S2: being added the aqueous polyurethane of isocyano sealing end in the dispersion liquid, and high-speed stirred obtains aqueous polyurethane/nitridation
Boron nano composite dope；
S3: by the aqueous polyurethane/boron nitride nanometer composite coating plastic film mulch, room temperature curing obtains aqueous polyurethane/boron nitride and receives
Rice compelx coating.
8. the preparation method of composite coating according to claim 7 and its film, which is characterized in that in the S1, surpass
The time of sound dispersion is 20~60 min.
9. the preparation method of composite coating according to claim 7 and its film, which is characterized in that high in the S2
The time of speed stirring is 30~60 min, and revolving speed is 500~2000 rpm.
10. the preparation method of composite coating according to claim 7 and its film, which is characterized in that, will in the S3
The aqueous polyurethane/boron nitride nanometer composite coating is laid on substrate, and the aqueous poly- ammonia is obtained after room temperature curing 1~3 day
Ester/boron nitride nanometer compelx coating.
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| CN111471156A (en) * | 2020-05-11 | 2020-07-31 | 黎哲华 | Insulating high-thermal-conductivity modified polyurethane film and preparation method thereof |
| CN112029262A (en) * | 2020-04-15 | 2020-12-04 | 重庆门朵新材料科技有限公司 | Boron nitride reinforced waterborne polyurethane high-thermal-conductivity high-barrier material and condom |
| CN112625569A (en) * | 2020-12-10 | 2021-04-09 | 淮阴工学院 | Preparation method of waterborne polyurethane/inorganic nano composite material coating with bionic micropatterning |
| CN112876978A (en) * | 2019-08-02 | 2021-06-01 | 江苏凯伦建材股份有限公司 | Preparation method of single-component root-puncture-resistant waterproof coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112876978A (en) * | 2019-08-02 | 2021-06-01 | 江苏凯伦建材股份有限公司 | Preparation method of single-component root-puncture-resistant waterproof coating |
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| CN112029262A (en) * | 2020-04-15 | 2020-12-04 | 重庆门朵新材料科技有限公司 | Boron nitride reinforced waterborne polyurethane high-thermal-conductivity high-barrier material and condom |
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| CN112625569A (en) * | 2020-12-10 | 2021-04-09 | 淮阴工学院 | Preparation method of waterborne polyurethane/inorganic nano composite material coating with bionic micropatterning |
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