Summary of the invention
The object of the invention is: in order to solve the problem, the invention provides a kind of water boiling resistance vibrin and preparation method thereof, carbonic acid ester bond is introduced in common water boiling resistance vibrin segment, under the prerequisite not affecting its water boiling resistance performance, substantially increase wear resistance and the weather resistance of water boiling resistance vibrin.
The technical scheme realizing the object of the invention is: a kind of water boiling resistance vibrin, and this resin prepares by the following method: by small molecules diprotic acid (acid anhydride), small molecules dibasic alcohol, organic polyhydric alcohol and polycarbonate diol carry out polycondensation.
Be specially following steps:
Small molecules dibasic alcohol, organic polyhydric alcohol are added in the reactor with heat riser and whipping appts; pass into nitrogen; intensification is heated to material and melts as liquid; add small molecules diprotic acid (acid anhydride), polycarbonate diol and esterifying catalyst more successively; continue under nitrogen protection to be warming up to water outlet; heat up in a steamer a temperature: 90-103 DEG C, temperature of reaction: 140-230 DEG C, preferably 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 230 DEG C.Reaction is to target acid number: 3-6mgKOH/g, and target Cone & Plate viscosity (175 DEG C): 10-13P, stopped reaction, can obtain the endurable polyester resin of water boiling resistance excellent performance.
The preparation method of above-mentioned water boiling resistance vibrin, described alkyd equivalence ratio is (1.1-1.3): 1 feeds intake, and preferred 1.15:1 or 1.2:1 or 1.3:1 feeds intake.
The preparation method of above-mentioned water boiling resistance vibrin, one in described esterifying catalyst tetrabutyl titanate, titanium isopropylate, lithium hydroxide, lead acetate, Dibutyltin oxide or Mono-n-butyltin, catalyzer is preferably lithium hydroxide or Dibutyltin oxide or Mono-n-butyltin.
The preparation method of above-mentioned water boiling resistance vibrin, described small molecules diprotic acid (acid anhydride) is preferably Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, one or more in hexanodioic acid.
The preparation method of above-mentioned water boiling resistance vibrin, described small molecules dibasic alcohol is preferably methyl propanediol, BDO, in 1.6-hexylene glycol, ethylene glycol, glycol ether, neopentyl glycol one or more.
The preparation method of above-mentioned water boiling resistance vibrin, described organic polyhydric alcohol is preferably TriMethylolPropane(TMP) or trimethylolethane.
The preparation method of above-mentioned water boiling resistance vibrin, described polycarbonate diol is UH-CARB50, UM-CARB90 (3/1) of Ube company, one or more of UM-CARB90 (1/1), more preferably UH-CARB50.
A kind of water boiling resistance vibrin, it is by the polymkeric substance formed after small molecules diprotic acid (acid anhydride), small molecules dibasic alcohol, organic polyhydric alcohol and polycarbonate diol polycondensation, is the product prepared by above-mentioned either method.
The present invention is based upon on the basis of environmental protection theory, through extensive and deep research, by the water boiling resistance vibrin formed after small molecules diprotic acid (acid anhydride), small molecules dibasic alcohol, organic polyhydric alcohol and polycarbonate diol polycondensation, the rosin products obtained is because having excellent water boiling resistance performance, antifriction scrape along weather resistance containing carbonic acid ester bond.
The present invention has positive effect: (1) the present invention introduces carbonic acid ester bond by polyreaction in water boiling resistance polyester resin structure, for water boiling resistance coating provides excellent wear resistance and weather resistance, does not affect the water boiling resistance performance of this resin simultaneously; (2) the present invention chooses most suitable temperature of reaction, reacts completely; (3) raw material that adopts of polyreaction of the present invention is all cheap is easy to get, and preparation method is simple to operation, and technological design is reasonable, is applicable to large-scale industrial production.
Embodiment
(embodiment 1)
In the reactor with agitator, temperature rising reflux device, add 400.6g methyl propanediol, 450.7g1,4-butyleneglycol and 272.8g TriMethylolPropane(TMP) open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 456.2g Tetra hydro Phthalic anhydride, 734.8g m-phthalic acid, 364.9g hexanodioic acid, 170gUH-CARB50 and 2.5g Mono-n-butyltin again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 220 DEG C; sampling and testing resinous acid value: 4.2mgKOH/g, when 175 DEG C of cone-plates glue for 10.9P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.Wherein alkyd feed ratio is 1.15:1.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 2)
In the reactor with agitator, temperature rising reflux device, add 262.5g ethylene glycol, 507.4g1,6-hexylene glycol and 639.2g tetramethylolmethane open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 412g Tetra hydro Phthalic anhydride, 778g m-phthalic acid, 700g sebacic acid, 250gUH-CARB90 (3/1) and 3.5g lithium hydroxide again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 230 DEG C; sampling and testing resinous acid value: 5.8mgKOH/g, when 175 DEG C of cone-plates glue for 12.8P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.Wherein alkyd feed ratio is 1.2:1.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 3)
In the reactor with agitator, temperature rising reflux device, add 215.9g propylene glycol, 375.9g neopentyl glycol and 412.8g trimethylolethane open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 356.2g terephthalic acid, 564.4g m-phthalic acid, 306.6g hexanodioic acid, 256.3gUH-CARB90 (1/1) and 4g tetrabutyl titanate again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 225 DEG C; sampling and testing resinous acid value: 3.5mgKOH/g, when 175 DEG C of cone-plates glue for 10.5P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.Wherein alkyd feed ratio is 1.3:1.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 4)
In the reactor with agitator, temperature rising reflux device, add 210.9g glycol ether, 410.5g methyl propanediol and 426.3g TriMethylolPropane(TMP) open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 456.9g Tetra hydro Phthalic anhydride, 589.1g terephthalic acid, 560.9g hexanodioic acid, 182gUH-CARB50 and 2.9g Dibutyltin oxide again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 225 DEG C; sampling and testing resinous acid value: 5.2mgKOH/g, when 175 DEG C of cone-plates glue for 11.8P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 5)
In the reactor with agitator, temperature rising reflux device, add 170.9g methyl propanediol, 410.2g neopentyl glycol and 460.5g trimethylolethane open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 412.5g Tetra hydro Phthalic anhydride, 890.5g m-phthalic acid, 540.1g sebacic acid, 300.9gUH-CARB90 (3/1) and 3.2g titanium isopropylate again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 215 DEG C; sampling and testing resinous acid value: 3.2mgKOH/g, when 175 DEG C of cone-plates glue for 12.3P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 6)
In the reactor with agitator, temperature rising reflux device, add 120.6g ethylene glycol, 256.8g propylene glycol and 548.2g tetramethylolmethane open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 894.5g Tetra hydro Phthalic anhydride, 245.9g m-phthalic acid, 500.6g hexanodioic acid, 400.2gUH-CARB90 (1/1) and 3.6g lithium hydroxide again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 230 DEG C; sampling and testing resinous acid value: 5.3mgKOH/g, when 175 DEG C of cone-plates glue for 12.6P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
Made respectively by water boiling resistance vibrin in embodiment 1 ~ 6 and have the water boiling resistance coating that thickness is 300-500 μm, by its physicals of following method evaluation, result is shown in Table 1.
In an embodiment, about the multiple physical properties of described elastic resin, test according to following test method.
1. water boiling resistance:
After 100 DEG C of boiling water boiling 45min, non-foaming, do not ftracture, do not change color as qualified.
2.RCA tests:
With RCA abrasion tester with 175gf, rub 250 times at water boiling resistance coatingsurface, it is qualified for not exposing ground.
3. weather resistance:
Formed and there is the water boiling resistance coating that thickness is 300-500 μm, this film is placed in accelerated aging test instrument (WEL-SUN-DC) after 360 hours, measure RCA Rubbing number by above-mentioned 2nd article of method.After measurement, durability evaluation is as described below: for qualified wherein said value is 70% or higher of the value measured in above-mentioned 2nd article.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.