CN102115534A - Dicyclopentadiene type unsaturated polyester modified by tung oil, and preparation method and application thereof - Google Patents

Abstract

The invention discloses a dicyclopentadiene type unsaturated polyester modified by tung oil, and a preparation method and application thereof. The method comprises the following steps: reacting raw materials maleic anhydride and dicyclopentadiene under the action of a catalyst to obtain dicyclopentadiene semi-maleate; adding dihydric alcohol, dibasic acid and polymerization inhibitor, and heating to 190-210 DEG C for dehydration and esterification; when the acid value reaches 50-120 mg KOH/g, cooling to 120-180 DEG C, adding a certain amount of tung oil, and heating to 200-210 DEG C to continue the reaction; and after the acid value reaches 20-35 mg KOH/g under the action of esterification, cooling to 100-120 DEG C, diluting with styrene dissolved with a small amount of polymerization inhibitor, and uniformly dispersing to obtain the product. The dicyclopentadiene type unsaturated polyester modified by tung oil according to the method has the advantages of favorable air-drying property, aging resistance, biodegradability and the like. The product is suitable to be used as an unsaturated polyester paint for corrosion protection, insulation and binding.

Description

Utilizing tung oil to modify dicyclopentadiene type unsaturated polyester and its preparation method and application

technical field

The invention belongs to a preparation method of new high molecular polymer materials, in particular to a preparation method of tung oil modified dicyclopentadiene type unsaturated polyester resin. The resin prepared by the method can be used in industries such as unsaturated polyester coatings.

Background technique

Polymer materials have a huge impact on human production and life. At present, its synthetic raw materials mainly depend on petroleum. However, the oil reserves on earth are only enough for a few decades at most. In order to find resources that can replace petroleum and protect the environment, it is wise to develop renewable resources. Vegetable oil is one of these resources. Due to its abundant reserves, biodegradability, and abundant chemically modifiable functional groups in its structure, more and more literatures have reported the use of vegetable oils to modify polymer materials. Among them, the unsaturated polyester (UPR) material modified by vegetable oil has also attracted the attention of many researchers.

As a unique natural renewable resource in my country (the output of tung oil in my country accounts for 80% of the world's output, with an annual output of more than 100,000 tons), tung oil is often only used for export and existing primary processing, and its comprehensive development and utilization is far from enough . In the past two years, the market demand for raw material tung oil has been sluggish, and the price of tung oil has dropped. Therefore, the development of tung oil deep processing technology can broaden the sales channels of tung oil and greatly increase the added value of tung oil products.

Tung oil is a drying oil and is capable of absorbing oxygen to crosslink. The main component of tung oil is glyceryl oleate, the structural formula is:

The oily ester molecule contains 3 conjugated double bonds. Among the mixed fatty acids contained in tung oil, there are 80% ericic acid (octadecatriene-[9,11,13]-acid). Specific to the reaction process, the unsaturated bonds and carboxyl groups contained in the structure of tung oil can be used to introduce various chemical reactions such as Diels-Alder reaction, Friedel-Crafts reaction, oxidation polymerization, free radical polymerization, amidation and esterification. To the preparation of general-purpose unsaturated polyester. Zhou Juxing (CN 86108060A), Li Juncheng ("Binding Agent" 1990, (2): 60) and Zhao Guiying ("Chemical Times" 2007, 21 (12): 31) etc. have reported respectively the unsaturated polymer after tung oil modification. Ester resin, with many advantages: toughening, air drying, corrosion resistance, aging resistance, biodegradability, etc.

On the other hand, dicyclopentadiene (DCPD) was introduced into the synthesis of unsaturated polyesters as early as the early 1980s. Dicyclopentadiene type unsaturated polyester resin has excellent properties, such as high hardness, air drying, chemical corrosion resistance, ultraviolet light resistance, excellent electrical properties and good adhesion to glass fiber, steel, etc. . However, due to the small molecular weight and high brittleness of this kind of resin, it has obvious disadvantages when used in unsaturated polyester coatings: the coating film is relatively brittle after curing, the greening is serious, and the thick coating is easy to whiten, etc. Therefore, in order to produce unsaturated polyester resin materials with excellent properties, it is necessary to be able to overcome the above-mentioned shortcomings.

Contents of the invention

The purpose of the present invention is to overcome the disadvantages of existing general-purpose unsaturated polyesters, such as long-term dependence on petrochemical raw materials, poor toughness, refractory degradation and poor air-drying property, which cannot meet the use requirements of unsaturated polyester coatings. Provided is a dicyclopentadiene type unsaturated polyester modified by tung oil and its preparation method and application, which have the advantages of easy operation, stable product quality and low cost.

The technical scheme of the present invention is: a kind of preparation method utilizing tung oil modified dicyclopentadiene type unsaturated polyester, comprises the following steps:

In the first step, react as follows:

In the second step, dibasic alcohol, dibasic acid and a conventional amount of polymerization inhibitor are added according to the metering ratio, and a fractionation column and a water separator are installed on the four-necked flask, and the temperature is raised to 150°C, and the temperature is kept for 0.5 to 1 hour. Raise the temperature to 190-210°C for dehydration and esterification, and control the temperature of the fractionation column to ≤105°C;

In the third step, when the acid value reaches 50-120mgKOH/g, cool down to 120-180°C and add tung oil according to the metering ratio, then raise the temperature to 200-210°C to continue the reaction, esterify to an acid value of 25-40mgKOH/g, and then cool to 100-120°C, add styrene dissolved in a polymerization inhibitor to dilute, and disperse evenly to obtain the product.

In the first step, a catalyst is added to react at 80-140°C in an oxygen-free environment. The catalyst is any one or more of phosphoric acid, dodecylbenzenesulfonic acid, and p-toluenesulfonic acid in any combination. than the formed mixture.

The dibasic acid is fumaric acid or phthalic anhydride or a mixture of the two.

The dihydric alcohol is any one of ethylene glycol, propylene glycol and diethylene glycol or a mixture of several in any proportion.

The polymerization inhibitor is any one of hydroquinone, p-benzoquinone, and 2,6-di-tert-butyl-p-cresol or a mixture formed in any proportion.

The general structural formula of the prepared tung oil modified dicyclopentadiene type unsaturated polyester is:

HO-CH₂-CH₂-O-CH₂-CH₂-，H-；R₂为：-CH₂-CH₂-，

-CH₂-CH₂-O-CH₂-CH₂-；R₃为：-CH＝CH-，

R₄为余下的桐油甘油酯加成物；m，n均为≥1的整数。 Wherein, R ₁ is: HO-CH ₂ -CH ₂ -,

HO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, H-; R ₂ is: -CH ₂ -CH ₂ -,

-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -; R ₃ is: -CH=CH-,

R ₄ is the remaining tung oil glyceride adduct; m, n are both integers ≥ 1.

The tung oil modified dicyclopentadiene type unsaturated polyester is used as an unsaturated polyester coating and as an anti-corrosion, insulation and adhesive.

Beneficial effect:

(1) The present invention adopts multi-step synthesis technology, which is easy to operate, stable in product quality, simple in process, easy to expand industrial production, and strong in practicability;

(2) The molecular weight of the resin of the present invention is relatively high, the number average molecular weight is 1100-1300; the acid value is stable, the acid value is 22.6-33.9mgKOH/g, and the product viscosity is 868-1430mPa·s. The obtained resin has air-drying properties, corrosion resistance and aging resistance, biodegradability, etc., and the mechanical and thermal properties of the material meet the requirements of general-purpose unsaturated polyester resin coatings.

(3) The modified materials used in the preparation method of the present invention are tung oil and DCPD, which are relatively low in price and are conducive to cost reduction. The cost is 3-10% lower than that of similar unmodified general-purpose unsaturated polyester resins.

Detailed ways

The following examples of the present invention are only used as a further description of the content of the present invention, and cannot be regarded as the content or scope of the present invention. Below in conjunction with embodiment the present invention is described in further detail.

The tung oil modified dicyclopentadiene type unsaturated polyester resin compound involved in the invention has a number average molecular weight of 1000-1300. Since there are many kinds of acids and alcohols contained therein, the molecular structural formula can be expressed by the following general formula:

In the formula

R ₁ is: HO-CH ₂ -CH ₂ -, HO- _CH2 - _CH2 -O- _CH2 - _CH2- , H-;

-CH₂-CH₂-O-CH₂-CH₂-；R ₂ is: -CH ₂ -CH ₂ -,

_-CH2 - _CH2 -O- _CH2 - _CH2- ;

R ₃ is: -CH=CH-,

R ₄ is the remaining tung oil glyceride adduct, here because tung oil is a triglyceride structure, so R ₄ also includes the reaction on the other two branched chains;

Both m and n are integers greater than or equal to 1.

The synthetic method of tung oil modified DCPD type unsaturated polyester resin involved in the present invention is as follows:

(1) Put the reaction raw materials maleic anhydride and dicyclopentadiene into the four-necked flask device with a reflux condenser according to the molar ratio of 0.8-1.2:1, and add the catalyst of 0.4-0.8% of the total weight of the material ; After passing the protective gas, heat up to 80-100°C and add a certain amount of water dropwise to control the temperature of the system below 140°C; Structural formula (I).

(2) Adding the metering ratio again means that the alkyd molar ratio of the whole material system is 2.05-2.15: 1 glycol, dibasic acid and the polymerization inhibitor of 0.05-0.1% of the total weight of the material, on the four-necked flask Install a fractionation column and a water separator, raise the temperature to 150°C, keep it warm for 0.5-1h, and then raise the temperature to 190-210°C for dehydration and esterification, and control the temperature of the fractionation column to ≤105°C to reduce the loss of low-boiling glycols.

(3) When the acid value reaches 50-120mgKOH/g, lower the temperature to 120-180°C and add tung oil in a metered ratio, then raise the temperature to 200-210°C to continue the reaction. Esterify to an acid value of 25-40mgKOH/g, then cool to 100-120°C, add a small amount of styrene dissolved in a polymerization inhibitor to dilute, and disperse evenly to obtain the product.

The dibasic acid is fumaric acid or phthalic anhydride; it can also be a mixture of fumaric acid and phthalic anhydride in any proportion.

The dihydric alcohol is any one of ethylene glycol, propylene glycol and diethylene glycol or a mixture of any two in any proportion.

The catalyst is any one of phosphoric acid, dodecylbenzenesulfonic acid and p-toluenesulfonic acid or a mixture of the two in any proportion.

The polymerization inhibitor is any one of hydroquinone, p-benzoquinone and 2,6-di-tert-butyl-p-cresol or a mixture of two in any proportion.

The added amount of said styrene is preferably 30-35% by weight of the synthesized polymer.

The synthesized tung oil modified dicyclopentadiene type unsaturated polyester resin is suitable for coatings, adhesives and the like.

The tung oil modified dicyclopentadiene type unsaturated polyester product prepared by the invention has a viscosity of 868-1430mPa·s, an acid value of 22.6-33.9mgKOH/g, and a number average molecular weight of 1100-1300.

Example 1:

Put 30g (0.3mol) of maleic anhydride, 40g (0.3mol) of dicyclopentadiene and 0.7g of phosphoric acid into a four-necked flask device with a reflux condenser, raise the temperature to 80-100°C with a protective gas, and add 5.4 g (0.3mol) of water, the temperature of the control system is lower than 140°C; after adding the water, keep it warm for 1.5-2h to obtain dicyclopentadiene maleic acid half ester. Then add 22.8g (0.3mol) propylene glycol, 21.2g (0.2mol) diethylene glycol, 7.4g (0.05mol) phthalic anhydride, 29g (0.25mol) fumaric acid and 0.09g terephthalic acid Diphenol, install a fractionation column and a water separator on a four-neck flask, raise the temperature to 150°C, heat up to 190-210°C for dehydration and esterification after 0.5-1h of heat preservation, and control the temperature of the fractionation column to ≤105°C to reduce the low boiling point loss of diols. When the acid value reaches about 70mgKOH/g, cool down to 140°C and add 5g of tung oil, then raise the temperature to about 200-210°C to continue the reaction; after esterification to an acid value of 28.6mgKOH/g, cool to 120°C and add 0.05g of p-benzene The 75g styrene monomer of diphenol is diluted, obtains the yellow tung oil modified DCPD type unsaturated polyester product. The viscosity was 1430 mPa·s, and the number average molecular weight was 1100.

Example 2:

The add-on of tung oil is increased to 10g, and other is with embodiment 1 (omitted). The final acid value was 22.4 mgKOH/g, the viscosity was 1328 mPa·s, and the number average molecular weight was 1100.

Example 3:

The add-on of tung oil is increased to 15g, and other is with embodiment 1 (omitted). The final acid value was 29.7 mgKOH/g, the viscosity was 1315 mPa·s, and the number average molecular weight was 1100.

Example 4:

The addition of tung oil is increased to 20g, and the amount of styrene is increased to 80g, and other is with embodiment 1 (omitted). The final acid value was 30.6 mgKOH/g, the viscosity was 1284 mPa·s, and the number average molecular weight was 1400.

Example 5:

The add-on of tung oil is increased to 25g, and the amount of styrene is increased to 80g, and other is with embodiment 1 (omitted). The final acid value was 22.6 mgKOH/g, the viscosity was 1226 mPa·s, and the number average molecular weight was 1100.

Embodiment 6:

The addition of tung oil is increased to 30g, and the amount of styrene is increased to 80g, and other is with embodiment 1 (omitted). The final acid value was 33.9 mgKOH/g, the viscosity was 868 mPa·s, and the number average molecular weight was 1100.

Embodiment 7:

The addition of tung oil is 20g, and the amount of phthalic anhydride increases to 14.8g (0.1mol), and the amount of fumaric acid decreases to 23.2g (0.2mol), and others are the same as in Example 1 (omitted). The final acid value was 31.2 mgKOH/g, the viscosity was 1354 mPa·s, and the number average molecular weight was 1300, respectively.

Embodiment 8:

The addition of tung oil is 20g, and the amount of phthalic anhydride increases to 22.2g (0.15mol), and the amount of fumaric acid decreases to 17.4g (0.15mol), and others are the same as in Example 1 (omitted). The final acid value was 29.2 mgKOH/g, the viscosity was 1328 mPa·s, and the number average molecular weight was 1000.

Embodiment 9:

The add-on of tung oil is 20g, adds 9.3g (0.15mol) ethylene glycol, and the amount of propylene glycol is reduced to 11.4g (0.15mol), and other is with embodiment 1 (omitted). The final acid value was 27.1 mgKOH/g, the viscosity was 1430 mPa·s, and the number average molecular weight was 1100, respectively.

Example 10:

Change catalyzer phosphoric acid into 0.9g dodecylbenzenesulfonic acid, other is with embodiment 1 (omitted). The final acid value was 30.5 mgKOH/g, the viscosity was 1333 mPa·s, and the number average molecular weight was 1000.

Example 11:

Change catalyzer phosphoric acid into 0.8g p-toluenesulfonic acid, other is with embodiment 1 (omitted). The final acid value was 23.7 mgKOH/g, the viscosity was 1265 mPa·s, and the number average molecular weight was 1000.

Example 12:

The polymerization inhibitor hydroquinone is changed into p-benzoquinone, and others are with embodiment 1 (omitted). The final acid value was 25.8 mgKOH/g, the viscosity was 1418 mPa·s, and the number average molecular weight was 1000.

Example 13:

The polymerization inhibitor hydroquinone is changed into 2,6-di-tert-butyl p-cresol, and the others are the same as in Example 1 (omitted). The final acid value was 26.7 mgKOH/g, the viscosity was 1302 mPa·s, and the number average molecular weight was 1000.

Examples 14-19:

Take 10g each of the samples of Examples 1-6, add 0.2g methyl ethyl ketone peroxide and 0.1g cobalt naphthenate, mix and coat on the tinplate sheet, and the post-treatment temperature of the sample is 80°C for 30min. A coating with gloss and good adhesion is obtained, and the coating has good water resistance, acid and alkali resistance. Then the coating film performance test was carried out, and the main curing performance indexes of the samples of Examples 1-6 were compared in Table 1.

The main curing performance index of table 1 embodiment 1-6 sample

Pilot projects experiment method example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Gel time (min) GB/T 7193-08 18.3 19.9 18.8 18.7 22.6 25.8 Surface dry time (min) GB 6753-86 55 50 50 45 50 40 Working time (min) GB/T 1728-79 120 130 120 110 130 110 80℃ thermal stability (h) GB/T 7193-08 4.5 3.5 3.5 3 3.5 3 Adhesion (level) GB/T 1720-79 2 1 1 2 2 2 Flexibility (mm) GB/T 6742-86 0.5 1 1 1 2 2

Examples 20-25:

Get each 100g of the samples of Examples 1-6, add 2g of benzoyl peroxide and 2.5g of freshly steamed N,N-dimethylaniline to solidify and form a film, and the post-treatment temperature of the sample is 80 degrees for 2 hours, and 150 degrees 2 hours. The main physical properties of the samples are compared in Table 2. It can be seen that its physical indicators all meet the film-forming requirements of general-purpose resins.

The main physical property index of table 2 embodiment 1-6 sample

Pilot projects experiment method example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Tensile strength (MPa) GB/T2568-95 60.2 56.8 54.2 53.3 46.7 46.9 Tensile modulus of elasticity (GPa) GB/T2568-95 2.85 2.67 2.63 2.47 2.23 1.98 Elongation at break (%) GB/T2568-95 3.9 4.2 4.8 4.9 5.7 6.8 Bending strength (MPa) GB/T2570-95 110.1 116.1 117.7 125.4 126.1 125.1 Flexural modulus of elasticity (GPa) GB/T2570-95 3.1 3.2 3.6 3.9 3.9 3.8 Impact strength (KJ/m ² ) GB/T2571-95 10.1 10.0 10.7 9.1 8.7 9.5 Heat distortion temperature (°C) GB 1634-04 73.3 70.2 66.8 67.5 61.2 62.3 Barcol Hardness GB 3854-83 38 36 32 37 29 26

The present invention is not limited to the above-mentioned embodiments, and all of the contents of the present invention can be implemented and have the above-mentioned good effects.

Claims (7)

1. a preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester is characterized in that, comprises the following steps:

The first step, press the following formula reaction:

In second step, than the stopper that adds dibasic alcohol, diprotic acid and convention amount again, on four-hole boiling flask, install fractional column and water trap additional by metering, be warming up to 150 ℃, insulation 0.5～1h is warming up to 190～210 ℃ of dehydration esterifications after the end, control fractional column temperature≤105 ℃;

The 3rd step, when acid number reaches 50～120mgKOH/g, be cooled to 120～180 ℃ by metering ratio adding tung oil, be warming up to 200～210 ℃ again and continue reaction, esterifications to acid number 25～40mgKOH/g postcooling to 100～120 ℃, add the vinylbenzene that is dissolved with stopper and dilute, being uniformly dispersed obtains product.

2. by the described preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1, it is characterized in that, add catalyzer 80～140 ℃ of reactions in oxygen-free environment in the described the first step, described catalyzer is any or several mixture that forms with any proportioning in phosphoric acid, Witco 1298 Soft Acid, the tosic acid.

3. by the described preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1, it is characterized in that described diprotic acid is FUMARIC ACID TECH GRADE or Tetra hydro Phthalic anhydride or both mixtures.

4. by the described preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1, it is characterized in that described dibasic alcohol is any or several mixture that forms with any proportioning in ethylene glycol, propylene glycol, the glycol ether.

5. by the described preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1, it is characterized in that: described stopper is Resorcinol, para benzoquinone, 2, any in the 6-di-tert-butyl methyl phenol or several mixture that forms with any proportioning.

6. the tung oil-modified dicyclopentadiene type unsaturated polyester of the described preparation method's preparation that utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1 is characterized in that general structure is:

Wherein, R ₁For: HO-CH ₂-CH ₂-,

HO-CH ₂-CH ₂-O-CH ₂-CH ₂-, H-:R ₂For :-CH ₂-CH ₂-,

-CH ₂-CH ₂-O-CH ₂-CH ₂-; R ₃For :-CH=CH-,

R ₄Tung oil glyceryl ester affixture for remainder; M, n be 〉=1 integer.

7. the described tung oil-modified dicyclopentadiene type unsaturated polyester of claim 6 is as unsaturated polyester coating with as the application of anticorrosion, insulation and binding agent.