A kind of di-o-chlorodiphenylamine methane modified castor oil polyol and preparation method thereof

Abstract

The invention discloses a dichlorodiphenylamine modified castor oil polyol, which is prepared from 730-750 parts by weight of castor oil, 160-180 parts of triol with side chain, 40-60 parts of dichlorodiphenylamine, 60-80 parts of trimellitic anhydride, and 0.8-1.5 parts of a color reducing agent. The invention screens various reaction raw material compositions and specific reaction steps through a large number of experiments, and the prepared modified castor oil polyol is matched with an isocyanate curing agent to make a road anti-skid coating, which can greatly shorten the non-stick tire drying time and improve the bonding strength, and has achieved good technical progress.

Description

Technical Field

[0001] The invention relates to di-o-chlorodiphenylamine methane modified castor oil polyol and a preparation method thereof. Background Art

[0002] With the rapid development of my country's economy, the number of cars has increased rapidly. In order to prevent and reduce the occurrence of safety accidents, anti-skid road coatings are used to lay anti-skid coatings on long and steep downhill slopes, steep slopes and sharp bends, tunnel entrances and exits, village entrances and exits, highway toll stations, sections with sudden changes in technical or grade indicators, speed bumps and emergency parking strips. The coating effectively shortens the braking distance and prevents the brake system from locking, reducing the rate of traffic accidents.

[0003] According to the material type, anti-skid road coatings can be divided into three categories: acrylic, epoxy and polyurethane. Although acrylic anti-skid coatings dry quickly, they have poor permeability and adhesion, and require an additional coating process, resulting in poor anti-skid performance; epoxy resins have good mechanical properties and strong adhesion, but poor low-temperature resistance, the coating will crack at low temperatures, and the fatigue resistance is poor; polyurethane has good mechanical properties, strong impact resistance, good toughness, excellent low-temperature resistance and excellent stability, and the coating has good low-temperature resistance. Among these three types of coatings, polyurethane coatings have the best comprehensive performance and are currently the mainstream of anti-skid road coatings.

[0004] The hydroxyl component polyol category of polyurethane coatings can be divided into three categories: polyether polyols, polyester polyols and modified castor oil polyols. Among these three categories, modified castor oil polyols are generally used because of their good permeability to the road surface and high bonding strength.

[0005] The existing modified castor oil polyol has the following disadvantages:

[0006] 1. This type of modified castor oil polyol polyurethane anti-slip coating has a non-stick drying time of about 3-6 hours, which is not suitable for some occasions with high requirements for construction time.

[0007] 2. This type of modified castor oil polyol polyurethane anti-skid coating has a 24-hour bonding strength between 3-6MPa. Now some anti-skid pavement construction sites require a 24-hour bonding strength between 6-10MPa.

[0008] In summary, although the existing modified castor oil polyol polyurethane anti-slip coating has good impact resistance, flexibility, low temperature resistance and excellent stability, it still needs to be improved in drying time and bonding strength performance. Summary of the invention

[0009] The purpose of the invention is to provide a modified castor oil polyol, which is used in combination with an isocyanate curing agent to make a road anti-skid coating, which has a stable reaction, good toughness, good wear resistance, fast drying, high strength and other comprehensive properties. Another purpose of the invention is to provide a preparation method thereof.

[0010] Technical solution: In order to achieve the above purpose, the technical solution adopted by the present invention is:

[0011] A di-o-chlorodiphenylamine methane-modified castor oil polyol is prepared from the following raw materials in parts by weight:

[0012] 730-750 parts of castor oil, 160-180 parts of triol with side chain, 40-60 parts of dichlorodiphenylamine methane, 60-80 parts of trimellitic anhydride, 0.8-1.5 parts of color reducing agent.

[0013] As a preferred embodiment, in the above-mentioned di-o-chlorodiphenylamine methane-modified castor oil polyol, the color reducing agent is at least one of hypophosphorous acid and triphenyl phosphite or a mixture thereof.

[0014] As a preferred embodiment, in the above-mentioned dichlorodiphenylmethane-modified castor oil polyol, the triol with a side chain is at least one of trimethylolpropane and trimethylolethane or a mixture thereof.

[0015] As a preferred embodiment, the above-mentioned dichlorodiphenylamine methane-modified castor oil polyol, the dichlorodiphenylamine methane is 3,3'-dichloro-4,4'-diaminodiphenylmethane, commonly known as MOCA.

[0016] As a preferred embodiment, in the above-mentioned di-o-chlorodiphenylamine-modified castor oil polyol, the castor oil is refined castor oil.

[0017] The method for preparing a di-o-chlorodiphenylamine-modified castor oil polyol of the present invention comprises the following steps:

[0018] Castor oil, triol with side chain and color reducing agent are put into a reaction kettle according to weight proportion, nitrogen is introduced, the temperature is raised to 235-245°C for heat preservation reaction for a period of time, the temperature is lowered to 180-190°C by nitrogen introduction, trimellitic anhydride is added, the temperature is raised to 200-220°C for heat preservation, nitrogen is turned off after liquid is discharged, the acid value is measured to be between 15-20, di-o-chlorodiphenylamine methane is added, the temperature is continued to be kept between 200-220°C, the acid value is measured to be between 5-8, vacuuming is started, samples are taken to measure the acid value, amine value and viscosity, the temperature is immediately lowered after the three items are qualified, cooling and packaging are carried out to obtain modified castor oil polyol.

[0019] Preferably, the preparation method of a di-o-chlorodiphenylamine modified castor oil polyol of the present invention comprises the following steps: taking castor oil, triol with side chain and color reducing agent by weight and putting them into a reaction kettle, passing nitrogen, heating to 235°C-245°C and keeping the temperature for 1.5 hours, passing nitrogen and cooling to 180°C, adding trimellitic anhydride, heating to 200°C-220°C and keeping the temperature, turning off nitrogen after liquid is discharged, and measuring the acid value to be between 15-20. Add di-o-chlorodiphenylamine methane, continue to keep warm between 200℃-220℃, measure the acid value between 5-8, start vacuuming for 1 hour, take samples to measure the acid value ≤5mgKOH / g, amine value: between 6-9mgKOH / g, viscosity: 40-50S / 25℃, format tube, immediately cool down after the three items are qualified, cool to about 100℃ and package to obtain di-o-chlorodiphenylamine methane modified castor oil polyol with 100% solid content.

[0020] The present invention mainly improves the deficiencies of existing castor oil polyols through the following schemes.

[0021] 1. The present invention has found through screening that, in castor oil polyol, polyacid trimellitic anhydride can improve the crosslinking density of polyol. Under the premise of the same oil length, the molecular weight is higher than that of ordinary castor oil polyol. When reacted with isocyanate, the prepared polyurethane coating has a tight structure, and the stronger the cohesion, the greater the bonding strength. The present invention has found that trimellitic anhydride cannot react with castor oil and polyol in one step. Castor oil must be firstly alcoholized with polyol, and then trimellitic anhydride is added to react. If the reaction is added in one step, the polyol prepared has particles, and it will be mixed after storage for a period of time, which affects the use. And the experimental screening found that the castor oil polyol prepared with pentaerythritol has a high crosslinking density and high bonding strength, but after being placed for two days, the castor oil polyol will be mixed, and the coating after the castor oil polyol after mixing and the isocyanate reaction has little bonding strength. Therefore, polyols cannot use pentaerythritol to improve the crosslinking density.

[0022] 2. The present invention has found through screening that in castor oil polyol, 4-6% of dichlorodiphenylamine and the residual carboxyl group of trimellitic anhydride are reacted to form amide bonds. The amide bonds have better adhesion to the road surface than ester bonds, which can greatly increase the bonding strength of the coating and achieve very good technical effects.

[0023] 3. The unique feature of the present invention in formula design is that part of the amino group of dichlorodiphenylamine is intentionally left. In the process, in the second step, trimellitic anhydride is first put into the reactor to react with the alcoholysis product. After the acid value is measured to be between 15-20, dichlorodiphenylamine is put into the reactor to continue the reaction, so that the amine value of the final product is controlled between 6-9 mgKOH / g. If dichlorodiphenylamine and trimellitic anhydride are put into the reactor together to react with the alcoholysis product, the amine value is difficult to control. The remaining amino group can accelerate the reaction of the prepared dichlorodiphenylamine modified castor oil polyol and isocyanate, thereby improving the dryness.

[0024] 4. The present invention screened triols with side chains and glycerol. The present invention preferably used triols with side chains instead of glycerol because the reaction of glycerol was not as stable as that of triols with side chains, the end point was more difficult to control, and the reaction reproducibility was poor.

[0025] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0026] The present invention screens out several raw materials including triol with side chain, trimellitic anhydride and dichlorodiphenylamine methane through a large number of experiments, and prepares dichlorodiphenylamine methane modified castor oil polyol through a three-step reaction process, which can greatly shorten the non-stick tire drying time and improve the bonding strength, thus achieving great technical progress. Specific embodiments

[0027] The embodiments of the present invention are described in detail below with reference to the examples. If no specific conditions are specified in the examples, the reaction is carried out according to conventional conditions or conditions recommended by the manufacturer. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0028] In the following examples, MOCA is di-o-chlorodiphenylamine methane, and refined castor oil was purchased from Wuxi Jinyu Oil Co., Ltd.

[0029] 1. The raw material compositions of the following examples are shown in Table 1:

[0030] Table 1 Raw material composition of each embodiment

[0031]

[0032] 2. The method for preparing the quick-drying high-performance alkyd resin of the present invention comprises the following steps:

[0033] According to the weight parts of the embodiments 1 to 5 in Table 1 above, the refined castor oil, the triol with side chain and the color reducing agent are put into the reaction kettle, nitrogen is passed, the temperature is raised to between 235°C and 245°C and kept for 1.5 hours, then the temperature is lowered to 180°C by nitrogen, trimellitic anhydride is added, the temperature is raised to between 200°C and 220°C and kept, the nitrogen is turned off after the liquid is discharged, the acid value is measured to be between 15-20KOH / g, dichlorodiphenylamine is added again, and the temperature is kept between 200°C and 220°C, and the acid value is measured to be between 5-8. Start to evacuate for 1 hour, take samples to measure the acid value ≤5mgKOH / g, amine value: between 6-9mgKOH / g, viscosity: 40-50S / 25°C (format tube), and immediately cool down after the three indicators are qualified, cool to about 100°C and package, and obtain the modified castor oil polyol with 100% solid content.

[0034] Comparative Example 1

[0035] Under the condition that the equipment is normal and clean, 773 parts by weight of refined castor oil, 186 parts of trimethylolpropane, 1.5 parts of hypophosphorous acid and 63 parts of phthalic anhydride are put into the reactor, the reflux valve is closed, nitrogen is passed, the temperature is raised to between 200°C and 220°C for insulation, the nitrogen is turned off after the liquid is discharged, and the acid value is between 5 and 8. Start vacuuming for 1 hour, take a sample to measure the acid value ≤5KOH / g, and the viscosity is 25-30S / 25°C (format tube). After passing the test, the temperature is immediately lowered, cooled to about 100°C and packaged to obtain the resin of Comparative Example 1.

[0036] Application Example 1

[0037] 1. Take the modified castor oil polyol obtained in the above Examples 1 to 5 and the castor oil polyol obtained in Comparative Example 1 and mix them according to the paint formula in Table 2 to prepare a paint:

[0038] Table 2 Paint formula

[0039] raw material Ratio (number of portions) Castor oil polyol (Examples 1 to 5 and Comparative Example 1) 300 Heavy Calcium 650 Solvent (xylene) 50

[0040] 2. Paint testing

[0041] The color paints prepared in the above Examples 1 to 5 and Comparative Example 1 and diphenylmethane cyanate (MDI) were prepared in a weight ratio of 100:18 to prepare a polyurethane coating, and the coating was tested as follows:

[0042] The specific paint test results are shown in Table 3:

[0043] Table 3 Polyurethane coating test results

[0044]

[0045] Note: 1. The above six types of polyurethane coatings were tested according to JT / T 712-2008 standard. The results all met the requirements of JT / T712-20084.1 and JT / T 712-20084.3, so they will not be repeated here.

[0046] The above experimental results show that the present invention screens various reaction raw material compositions through a large number of experiments, especially through the compatibility of trimellitic anhydride, dichlorodiphenylamine methane and triol with side chain, and through a three-step reaction process, the modified castor oil polyol is prepared. The polyurethane anti-skid road coating made of the modified castor oil polyol not only meets the general physical and chemical properties of road anti-skid coatings (JT / T 712-20084.1) and the specific physical and chemical properties requirements of cold-coated road anti-skid coatings (JT / T712-20084.3), but most importantly, the non-stick tire drying time of the polyurethane road anti-skid coating is increased from 3-6 hours to within 80 minutes; the bonding strength of the polyurethane road anti-skid coating is increased from 3-6MPa to more than 7MPa. The shortcomings of the prior art are overcome and good technical effects are achieved.

Claims

1. A di-o-chlorodiphenylamine-modified castor oil polyol, characterized in that: It is made of the following raw materials in parts by weight: 730-750 parts of castor oil, 160-180 parts of triol with side chain, 40-60 parts of dichlorodiphenylamine methane, 60-80 parts of trimellitic anhydride, 0.8-1.5 parts of color reducing agent.

2. A castor oil polyol modified by di-o-chlorodiphenylamine methane according to claim 1, characterized in that: The color reducing agent is at least one of hypophosphorous acid and triphenyl phosphite or a mixture thereof.

3. A castor oil polyol modified by di-o-chlorodiphenylamine methane according to claim 1, characterized in that: The triol with a side chain is at least one of trimethylolpropane and trimethylolethane or a mixture thereof.

4. The di-o-chlorodiphenylamine modified castor oil polyol according to claim 1, characterized in that: The di-o-chlorodiphenylamine methane is 3,3'-dichloro-4,4'-diaminodiphenylmethane.

5. The method for preparing a di-o-chlorodiphenylamine modified castor oil polyol according to any one of claims 1 to 3, characterized in that: The following steps are involved: Castor oil, triol with side chain and color reducing agent are put into a reaction kettle according to weight proportion, nitrogen is introduced, the temperature is raised to 235-245°C for heat preservation reaction for a period of time, the temperature is lowered to 180-190°C by nitrogen introduction, trimellitic anhydride is added, the temperature is raised to 200-220°C for heat preservation, nitrogen is turned off after liquid is discharged, the acid value is measured to be between 15-20, di-o-chlorodiphenylamine methane is added, the temperature is continued to be kept between 200-220°C, the acid value is measured to be between 5-8, vacuuming is started, samples are taken to measure the acid value, amine value and viscosity, the temperature is immediately lowered after the three items are qualified, cooling and packaging are carried out to obtain modified castor oil polyol.

6. The method for preparing a di-o-chlorodiphenylamine modified castor oil polyol according to claim 5, characterized in that: The following steps are involved: Castor oil, triol with side chain and color reducing agent are put into a reaction kettle according to weight proportion, nitrogen is introduced, the temperature is raised to 235-245°C and kept for 1.5 hours, the temperature is lowered to 180°C by nitrogen introduction, trimellitic anhydride is added, the temperature is raised to 200-220°C and kept, the nitrogen is turned off after the liquid is discharged, the acid value is measured to be between 15-20, di-o-chlorodiphenylamine methane is added, the temperature is kept between 200-220°C, the acid value is measured to be between 5-8, vacuum is started for 1 hour, and samples are taken to measure the acid value ≤5mgKOH / g, the amine value: between 6-9mgKOH / g, the viscosity: 40-50S / 25°C, a format tube is used, the temperature is lowered immediately after the three items are qualified, the mixture is cooled to 100°C and packaged to obtain modified castor oil polyol.

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