CN107936814A - The net taste woodcare paint of high hardness polyurethane that a kind of POSS is modified - Google Patents

Abstract

The invention relates to a POSS-modified high-hardness polyurethane odor-cleaning wood lacquer, which is composed of two components A and B, and the weight ratio of components A and B is 1.4-1.8:1; Resin, various auxiliary agents and solvents; component B is POSS modified low free monomer polyurethane curing agent; the invention also provides a preparation method of POSS modified low free monomer polyurethane curing agent. A POSS-modified high-hardness polyurethane net-odor wood paint prepared by the invention has excellent adhesion, fullness, high hardness, water resistance, flexibility, transparency, wear resistance, heat resistance, Pollution resistance and flame retardancy; it does not contain aromatic ketones or heavy metals, and has a deodorizing effect after 48 hours of film formation. It is an environmentally friendly polyurethane wood lacquer with deodorizing properties.

Description

A POSS-modified high-hardness polyurethane odor-cleaning wood varnish

technical field

The invention relates to a polyurethane wood varnish, in particular to a POSS-modified high-hardness polyurethane wood varnish with clean odor, which belongs to the technical field of wood coatings.

Background technique

With the improvement of people's material and cultural living standards, consumers have higher and higher requirements for the coating effect of furniture, which has led to the rapid growth of domestic wood coatings. In the furniture coating market, American-style painted furniture occupies a relatively large market share. Most of the domestic furniture industry uses color essence (a metal complex dye, such dyes have serious problems such as heavy metals exceeding the standard, containing pathogenic substances, temperature resistance, Poor light fastness and migration resistance, commonly known as Grace) for wood grain wiping and varnishing colorants, most of the resins used for wiping are ordinary alkyd resins and linseed oils, and the furniture still remains for a long time after painting. Odor; today's huge wood paint market has higher and higher requirements for paint products. Especially wood polyurethane (PU) paint has excellent comprehensive performance and is widely used by consumers, but there are many shortcomings in the product, such as whitening and blistering , delamination, non-scratch resistance, ghosting, fingerprints are not easy to disappear, etc.

Chinese patent CN104099000A discloses a benzene-free and odor-free anti-scratch PU matte varnish, which is composed of a component A resin paint and a component B curing agent. The weight ratio of components A and B is 1:0.5; The lacquer is composed of benzene-free, odor-free, anti-scratch alkyd resin, aldehyde and ketone resin, matting powder, auxiliary agent and solvent without vegetable oil (fatty acid); component B is composed of curing agent and solvent. The benzene-free odor-free anti-scratch PU matte varnish prepared by the invention does not contain aromatic hydrocarbons, ketones, heavy metals, vegetable oils (fatty acids), and no uncomfortable smell remains after 48 hours of film formation. It is an environment-friendly odor-free PU wood varnish.

However, existing polyurethane wood lacquers have defects such as poor crosslink density between the resin and the curing agent, poor hydrophobicity, poor heat resistance, and low flame retardancy.

Contents of the invention

The invention aims to provide a POSS-modified high-hardness polyurethane clean-odor wood varnish.

POSS, also known as cage-type polysilsesquioxane, is an inorganic core composed of silicon-oxygen skeletons connected alternately by Si-O. It is shaped like a "cage" and belongs to nano-compounds. The diversity, high activity and good polymer compatibility of POSS groups make it possible to introduce them into polymer materials by both physical blending and chemical copolymerization.

The curing agent used in the present invention is POSS-modified low-free monomer polyurethane curing agent, which is highly cross-linked and cured with hydroxyl-containing resins, and the paint film has high fullness, high wear resistance, heat resistance, water resistance and pollution resistance. sex.

In order to overcome the shortcomings and deficiencies of the prior art, the present invention adopts the following technical scheme, a kind of POSS modified high-hardness polyurethane odor-cleaning wood lacquer of the present invention, is made of A, B two components, A, B component The weight ratio is 1.4-1.8:1; the A component, by weight percentage, consists of: 50.0-85.0% of hydroxyl-containing deodorizing resin, 0.2-2.0% of wetting and dispersing agent, 0.1% of leveling agent ～1.0%, rheological additive 0.3～5.0%, defoamer 0.1～0.5%, functional additive 0～6.0%, solvent 12.0～40.0%; the B component is POSS modified low free monomer Polyurethane curing agent.

The low free monomer polyurethane curing agent modified by POSS is centered on cage polysilsesquioxane and contains 16 isocyanate groups. Its molecular structural formula is as follows:

Described POSS modified low free monomer polyurethane curing agent, its preparation steps are as follows:

a) Synthesis of isocyanate trimer: under the protection of _N2 , add 100.0 parts of isocyanate monomer, 0.05-0.1 parts of catalyst, 30.0-60.0 parts of solvent into the reaction kettle, start stirring to stir the materials evenly, and heat to 50-80 After reacting at ℃ for 2 to 4 hours, add 5.0 parts of the mixed solution containing catalyst, accelerator and solvent dropwise, and finish adding in 0.5 hours, then keep the temperature at 50 to 80 ℃ to continue the reaction, and check the NCO value every 0.5 hours. When the detected NCO value is 10% to 7%, immediately add a polymerization inhibitor accounting for 0.1 to 0.5% of the mass of the isocyanate monomer and cool down to 20°C to obtain the isocyanate trimer;

b) Synthesis of POSS-modified low-free monomer polyurethane curing agent: at room temperature, add a mixture of 15.0 to 40.0 parts of octaaminophenyl POSS and 30.0 parts of solvent dropwise to the isocyanate trimer solution, the dropwise addition is completed in 0.5 to 1 hour, and the reaction is continued for 2 to 3 hours to obtain the POSS-modified low free monomer polyurethane curing agent.

Wherein, the isocyanate monomer is at least one of TDI, MDI, NDI, TODI, HDI, TMDI, XDI, IPDI, HMDI, HTDI.

The mixed solution containing catalyst, accelerator and solvent is composed of: catalyst 2.0%-10.0%, accelerator 2.0%-10.0%, solvent 80.0%-96.0%.

Described catalyst is dibutyltin dilaurate, lithium acetate, tri-n-butyl phosphorus, stannous octoate, tin naphthenate, lead naphthenate, cobalt naphthenate, dibutyltin maleate, dibutyltin diacetate, At least one of triethylamine, K-1000, and benzyl glycidyl ether.

The accelerator is at least one of N,N-dimethyl-p-toluidine, N-methylpyrrole, triethanolamine and N,N-dimethyl-p-toluenesulfonyl chloride.

The hydroxyl-containing deodorizing resin is deodorizing alkyd resin, deodorizing polyester resin or hydroxy acrylic resin.

The wetting and dispersing agent described is polycarboxylic acid high molecular polymer containing amine derivatives, high molecular polyether compound containing pigment affinity group, polycarboxylic acid amide salt, polyhydroxyacid organic amine charge-neutral salt at least one of .

The leveling agent is titanate modified silicone leveling agent, titanate modified polyacrylate leveling agent, silicone modified acrylic leveling agent, fluorine modified acrylic leveling agent, silicon oxygen polymerization At least one of logistics leveling agents.

The rheological additive is at least one of nanoscale fumed silica, modified urea polymer, and polyamide wax.

The solvent is ethyl acetate, butyl acetate, sec-butyl acetate, 120 white oil, D40 dearomatization solvent, diethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, 3-methyl At least one of methyl oxypropionate.

The functional auxiliary agent is a matting agent, a hardening agent, an anti-scratch agent, an anti-blocking agent, an abrasion-resistant agent, and an ultraviolet absorber.

The defoamer is at least one of modified silicone defoamer and polyacrylate defoamer.

Compared with other technologies in the art, a kind of POSS modified high-hardness polyurethane net odor wood varnish of the present invention has the following advantages: (1) because the curing agent single molecule that adopts contains 16 isocyanate groups, and resin molecule When the -OH is cured, the crosslinking density is high, and the coating film can obtain high adhesion, high fullness, high hardness, and high water resistance; (2) Because the curing agent contains POSS groups, the coating film can obtain excellent hydrophobicity , flexibility, transparency, abrasion resistance, heat resistance, pollution resistance and flame retardancy. (2) It adopts odor-cleaning resin and low-free monomer polyurethane curing agent, does not contain aromatic ketones, does not contain heavy metals, and has a net-odor effect after 48 hours of film formation. It is an environmentally friendly polyurethane wood-cleaning paint.

Detailed ways

Below in conjunction with embodiment a kind of POSS modified high hardness polyurethane net odor wood lacquer of the present invention is further described. It should be understood that the specific embodiments described here are only used to explain related inventions, rather than to limit the invention.

Example 1

A kind of POSS modified low free monomer polyurethane curing agent A, its preparation steps are as follows:

a) Synthesis of isocyanate trimer: under the protection of N ₂ , add 100.0 parts of IPDI monomer, 0.1 part of tri-n-butylphosphine, and 30.0 parts of ethyl acetate to the reaction kettle, start stirring to stir the materials evenly, and heat to 80 After reacting at ℃ for 2 hours, 5.0 parts of ethyl acetate solution containing 2% tri-n-butylphosphine and 2% N-methylpyrrole were added dropwise, and the addition was completed in 0.5 hours, and then kept at 80°C to continue the reaction. Detect the NCO value once every 0.5 hours. When the detected NCO value is 9.0±0.5%, immediately add a polymerization inhibitor accounting for 0.5% of the mass of the isocyanate monomer and cool down to 20°C to obtain the isocyanate trimer;

b), the synthesis of POSS-modified low-free monomer polyurethane curing agent: at normal temperature, to the isocyanate trimer, add 19.2 parts of octaaminophenyl POSS and 30.0 parts of ethyl acetate solution dropwise, After the dropwise addition was completed in 1 hour, the reaction was continued for 2 hours to obtain the POSS-modified low free monomer polyurethane curing agent A.

Example 2

A kind of POSS modified low free monomer polyurethane curing agent B, its preparation steps are as follows:

a) Synthesis of isocyanate trimer: under the protection of _N2 , add 100.0 parts of HDI monomer, 0.1 part of K-1000, and 60.0 parts of isopropyl acetate into the reaction kettle, start stirring to stir the materials evenly, and heat to 80°C After reacting for 4 hours, add 5.0 parts of isopropyl acetate solution containing 10% K-1000 and 6% triethanolamine drop by drop, complete the dropwise addition in 0.5 hours, then keep at 80°C to continue the reaction, and detect NCO every 0.5 hours value, when the detected NCO value is 8.0±0.5%, immediately add a polymerization inhibitor accounting for 0.3% of the mass of the isocyanate monomer and cool down to 20°C to obtain the isocyanate trimer;

b), the synthesis of POSS-modified low-free monomer polyurethane curing agent: at room temperature, in the isocyanate trimer, add 21.6 parts of octaaminophenyl POSS and 30.0 parts of isopropyl acetate solution dropwise , After 1h dropwise addition, continue to react for 3h to obtain the POSS-modified low-free monomer polyurethane curing agent B.

Example 3

A POSS-modified high-hardness polyurethane odor-cleaning wood lacquer, which is composed of A and B components, the weight ratio of A and B components is 1.8:1; A component is composed of: 75.0 parts of saturated polyester resin, amine-derived 0.5 parts of polycarboxylic acid polymer dispersant, 0.3 parts of silicone modified acrylic leveling agent, 3.0 parts of nanoscale fumed silica, 21.0 parts of ethyl acetate, and 0.2 parts of modified silicone defoamer; The B component is: 55.0 parts POSS modified low free monomer polyurethane curing agent A.

Example 4

A POSS-modified high-hardness polyurethane odor-cleaning wood lacquer, consisting of two components A and B, the weight ratio of components A and B is 1.67:1; component A is composed of: 70.0 parts of odor-cleaning alkyd resin, polymer 1.0 parts of wetting and dispersing agent, 0.4 parts of fluorine-modified acrylic leveling agent, 3.0 parts of modified urea polymer rheology additive, 18.0 parts of ethyl acetate, 5.0 parts of propylene glycol butyl ether, 2.5 parts of matting agent, modified silicon 0.1 part of oxane defoamer; the B component is 60.0 parts of POSS modified low free monomer polyurethane curing agent B.

Example 5

A POSS-modified high-hardness polyurethane odor-cleaning wood lacquer, consisting of two components A and B, the weight ratio of A and B components is 1.75:1; component A is composed of 80.0 parts of hydroxyl acrylic resin, polymer wetting 0.5 parts of dispersant, 0.3 parts of silicone polymer leveling agent, 1.5 parts of polyamide wax, 14.0 parts of butyl acetate, 3.6 parts of methyl 3-methoxy propionate, 0.1 part of polyacrylate defoamer; the B The components are: 57.0 parts of POSS modified low free monomer polyurethane curing agent B.

With the two-component polyurethane wood coating in embodiment 3,4,5 and the net odor two-component polyurethane wood coating (comparative example) on the market, spray on the wood surface by construction requirements, after drying 24h, detect according to relevant standards, Its test data are shown in Table 1:

Table 1 Polyurethane wood coating performance technical indicators

Although the present invention has been described in detail and examples have been cited, for those of ordinary skill in the art, it is obvious that various solutions, modifications and changes that can be made according to the above description should be included within the scope of the claims .

Claims (9)

1. a POSS-modified high-hardness polyurethane clean-odor wood varnish, is characterized in that: the high-hardness polyurethane clean-odor wood varnish of described POSS modification, is made of A, B two components, A, B component The weight ratio is 1.4-1.8:1; the A component, by weight percentage, is composed of: 50.0-85.0% of hydroxyl-containing deodorizing resin, 0.2-2.0% of wetting and dispersing agent, and 0.1-2.0% of leveling agent. 1.0%, rheology additive 0.3-5.0%, defoamer 0.1-0.5%, functional additive 0-6.0%, solvent 12.0-40.0%; the B component is POSS modified low free monomer polyurethane Hardener; Wherein, the POSS modified low-free monomer polyurethane curing agent is centered on cage polysilsesquioxane and contains 16 isocyanate groups, and its molecular structure is as follows: Its preparation steps are as follows: a) Synthesis of isocyanate trimer: under the protection of _N2 , add 100.0 parts of isocyanate monomer, 0.05-0.1 parts of catalyst, 30.0-60.0 parts of solvent into the reaction kettle, start stirring to stir the materials evenly, and heat to 50-80 After reacting at ℃ for 2 to 4 hours, add 5.0 parts of the mixed solution containing catalyst, accelerator and solvent dropwise, and finish adding in 0.5 hours, then keep the temperature at 50 to 80 ℃ to continue the reaction, and check the NCO value every 0.5 hours. When the detected NCO value is 10% to 7%, immediately add a polymerization inhibitor accounting for 0.1 to 0.5% of the mass of the isocyanate monomer and cool down to 20°C to obtain the isocyanate trimer; b) Synthesis of POSS-modified low-free monomer polyurethane curing agent: at room temperature, add a mixture of 15.0 to 40.0 parts of octaaminophenyl POSS and 30.0 parts of solvent dropwise to the isocyanate trimer Liquid, dropwise in 0.5～1h, continue to react for 2～3h, obtain described POSS modified low free monomer polyurethane curing agent; The free monomer content in the POSS modified low free monomer polyurethane curing agent is less than 0.5%. 2. The POSS-modified high-hardness polyurethane odor-cleaning wood varnish according to claim 1, characterized in that: the hydroxyl-containing odor-cleaning resin is an odor-clean alkyd resin, a polyester resin with a clean odor or a hydroxyacrylic resin. 3. the high-hardness polyurethane net odor wood lacquer of POSS modification according to claim 1 is characterized in that: described isocyanate monomer is TDI, MDI, NDI, TODI, HDI, TMDI, XDI, IPDI, HMDI or At least one of HTDI. 4. the high-hardness polyurethane net odor wood lacquer of POSS modification according to claim 1 is characterized in that: described mixed solution containing catalyzer, promotor and solvent, by mass percentage, it is composed of: catalyst 2.0 %～10.0%, Accelerator 2.0%～10.0%, Solvent 80.0%～96.0%. 5. the high-hardness polyurethane net odor wood lacquer of POSS modification according to claim 1 is characterized in that: described catalyzer is dibutyl tin dilaurate, lithium acetate, tri-n-butyl phosphorus, stannous octoate, cyclic At least one of tin alkanoate, lead naphthenate, cobalt naphthenate, dibutyltin maleate, dibutyltin diacetate, triethylamine, K-1000 or benzyl glycidyl ether. 6. the high-hardness polyurethane net odor wood lacquer of POSS modification according to claim 1 is characterized in that: described accelerator is N, N-dimethyl-p-toluidine, N-methylpyrrole, triethanolamine Or at least one of N,N dimethyl-p-toluenesulfonyl chloride. 7. the POSS modified high-hardness polyurethane odor-cleaning wood lacquer according to claim 1, is characterized in that: described wetting and dispersing agent is polycarboxylate macromolecular polymer containing amino group derivative, containing pigment affinity At least one of polymer polyether compound, polycarboxylic acid amide salt or polyhydroxyacid organic amine electrically neutral salt; the leveling agent is titanate modified silicone leveling agent, titanic acid At least one of ester-modified polyacrylate leveling agent, silicone-modified acrylic leveling agent, fluorine-modified acrylic leveling agent or silicone polymer leveling agent; the rheological additive is a nanoscale gas phase At least one of silica, modified urea polymer or polyamide wax; the defoamer is at least one of modified silicone defoamer or polyacrylate defoamer. 8. the POSS modified high-hardness polyurethane net odor wood lacquer according to claim 1 is characterized in that: described functional auxiliary agent is matting agent, hardening agent, anti-scratch agent, anti-blocking agent, wear-resisting agent solvents or UV absorbers. 9. according to claim 1 and 4 described POSS modified high-hardness polyurethane net odor wood lacquers, it is characterized in that: described solvent is ethyl acetate, butyl acetate, sec-butyl acetate, 120 white oil, D40 At least one of dearomatization solvent, diethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, and methyl 3-methoxypropionate.