CN1772829A

CN1772829A - High stability colorless rosin pentaerythritol ester and preparation method thereof

Info

Publication number: CN1772829A
Application number: CN 200510095092
Authority: CN
Inventors: 高宏; 宋湛谦; 商士斌; 王振洪; 饶小平
Original assignee: Institute of Chemical Industry of Forest Products of CAF
Current assignee: Institute of Chemical Industry of Forest Products of CAF
Priority date: 2005-10-28
Filing date: 2005-10-28
Publication date: 2006-05-17
Anticipated expiration: 2025-10-28
Also published as: CN100358959C

Abstract

The present invention discloses one kind of high stability color-less rosin pentaerythrite ester with Hason color number smaller than 150, color change after being set in a drying tank at 180 deg.c for 8 hr not greater than 1 Ghana color number and color change after being irradiated with ultraviolet lamp for 15 hr not greater than 3 Ghana color number. Its preparation process includes the following steps: distilling rosin to obtain refined rosin; adding pentaerythritol, decolorizing agent, antioxidant and catalyst to refined rosin for esterification until reaching acid value lower than 20 mg/g; decompressing to eliminate low boiling point matter; cooling, adding heat stabilizer and light stabilizer via stirring to obtain the high stability color-less rosin pentaerythrite ester. The present invention has simple technological process and low production cost.

Description

High stability color-less rosin pentaerythrite ester and preparation method thereof

Technical field

The present invention relates to a kind of pentalyn and preparation method thereof, relate in particular to a kind of high stability color-less rosin pentaerythrite ester and preparation method thereof.

Background technology

Rosin ester is a kind of rosin deep processed product that is obtained by rosin and polyol reaction, so far the history in existing more than 70 year.It is of many uses, can be used as the tackifier of wrapping material, pressure sensitive adhesive, hot melt adhesive etc., the properties-correcting agent of rubber and plastics, the setting agent of makeup etc.

In a lot of Application Areass, the color of rosin ester and stability are the important indicators of its a market viability of decision.Since the seventies, carried out a large amount of research aspect production pale rosin and the carboxylate thereof both at home and abroad.Nearly two kinds of method: with U.S. Pat 5,395,920 are the method for representative, are to obtain colourless rosin ester by nilox resin is refining, esterification, dehydrogenation.This carboxylate (less than No. 1, Ghana) of light color and remaining on store and hot procedure in colour-change little.But its complex manufacturing, cost are higher.Second method is to select effect catalyzer preferably for use, disclose as EP0270773, EP0257622, US744925, US4650607, US 4643848 etc. and to have selected Hypophosporous Acid, 50 and Hypophosporous Acid, 50 alkaline earth salt or composite as esterifying catalyst for use, can shorten the reaction times, improve product color and improve oxidative stability with phenols sulfide.The third method is to obtain the rosin ester of light color by adding discoloring agent, has invented in esterification process or esterification finishes the back and adds the carboxylate that Organophosphorous compounds with decolorization, sulfide etc. obtain light color as JP9143430, JP8209070, US5504152, US 5387669, US 5387669, WO0006657 etc.; But the rosin esterification thing that these methods obtain still can not satisfy the requirements at the higher level of people to esterified prod at aspects such as color and thermostability, weather resisteants.

Summary of the invention

The invention provides the simple easy handling of a kind of technology, production cost is lower, product colour is shallow, the high stability color-less rosin pentaerythrite ester of thermostability and good weatherability and preparation method thereof.

The present invention adopts following technical scheme:

A kind of high stability color-less rosin pentaerythrite ester, the Ha Sense of this color of resin number less than No. 150; Thermostability: place 8h in 180 ℃ of air dry ovens, colour-change is not more than 1 Ghana's look number; Weather resisteant: under 20 ℃, apart from the following irradiation 15h of 500W ultraviolet lamp 50cm, rate of body weight gain is not more than 0.2%, and colour-change is not more than 3 Ghana's looks number.

A kind of preparation method of high stability color-less rosin pentaerythrite ester comprises the steps:

The first step, superfine rosin is 0～1kPa in vacuum tightness, and 180～270 ℃ of temperature are distillation down, and Ghana's look of producing color number is not more than No. 3, and acid number is 160mg/g～190mg/g, softening temperature is 70 ℃～85 ℃ a resin;

Second step, under inert atmosphere protection, in resin, add tetramethylolmethane and the discoloring agent that accounts for resin quality 0.1～1.0%, the anthraquinone that accounts for resin quality 0.01～0.1% that accounts for resin quality 11.0～16.0%, the catalyzer that accounts for resin quality 0.1～0.5% as oxidation inhibitor, under 230～290 ℃, carry out esterification, react to acid number and finish less than 20mg/g; Wherein, discoloring agent is 4,4-thiobis-(6 band butyl meta-cresol) or 4, and the mixture of one or more in 6-pair-(dodecyl sulfo-)-ortho-cresol or the nonyl phenol two sulphur oligopolymer, the proportioning of mixture can be any proportioning; Catalyzer is the one or more kinds of mixtures in ZnO, Mgo or the sterically hindered phenol phosphate compounds, and the proportioning of mixture can be any proportioning,

In the 3rd step, with the decompression of above-mentioned reaction product atmosphere of living in, and to keep vacuum tightness be 0～2kPa, and the hold-time is 0.5～2h, to remove low boilers;

The 4th step, the reaction product of removing low boilers is cooled to 200～230 ℃, add the thermo-stabilizer account for resin quality 0.1～1.0% and account for the photostabilizer of resin quality 0.1～1.0% and stir, obtain high stability color-less rosin pentaerythrite ester; Wherein, thermo-stabilizer is 2,5-ditert-butylhydro quinone or 2,6-di-tert-butyl-4-methy phenol or tricresyl phosphite (nonyl phenyl ester) or three (2, the 4-di-tert-butyl-phenyl) the one or more kinds of mixtures in phosphorous acid ester or the triphenyl phosphite, the proportioning of mixture can be any proportioning, photostabilizer is Succinic Acid and (4-hydroxyl-2,2,6,6-tetramethyl--1-sends pyridine alcohol) polymkeric substance or one or more the mixture in 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole or the Octabenzone, the proportioning of mixture can be any proportioning.

The present invention obtains following technique effect:

1. the simple easy handling of technology, production cost is lower: with U.S. Pat 5,395,920 are the method for representative, are to obtain colourless rosin ester by nilox resin is refining, esterification, dehydrogenation.Its complex manufacturing, cost are higher.

2. more shallow, thermostability of product colour and weathering resistance are better:

Table 1

Index	Color (Ha Sense number)	Thermostability (adding the nanofarad colorimetric)	Weathering resistance
			Weathering resistance		Rate of body weight gain (%)	Number variation of Ghana's look
			Product of the present invention	＜150	Rate of body weight gain (%)	Number variation of Ghana's look	＜1	＜0.20	3
Existing identical cost product	＞300	＞3	Product of the present invention	＜150	＞1.0	＞3	＜1	＜0.20	3

It is raw material that the present invention adopts the more shallow resin of color, in esterification process, carry out, adopt activity catalyzer preferably, reaction times can be shortened, adopt discoloring agent can further improve color, adopt oxidation inhibitor can prevent that oxidation makes color burn in the esterification process, comprehensive above several method makes the product colour that makes more shallow.Later stage adds thermo-stabilizer and photostabilizer, makes product have good use properties, i.e. thermostability and good weatherability.

In the prior art scheme, what have does not adopt these methods, and what perhaps have just adopts wherein one or more methods, so the product that obtains can not reach effect of the present invention aspect color and thermostability, the weathering resistance simultaneously.

With U.S. Pat 5,395,920 are the method for representative, and the color of its product and thermostability, weathering resistance can reach effect of the present invention, but its complex manufacturing, and cost is higher.

Pentalyn is to utilize carboxyl in the rosin and the hydroxyl in the tetramethylolmethane to carry out pure acid-respons to obtain.By adding discoloring agent, oxidation inhibitor, improved the color of product, add thermo-stabilizer, photostabilizer, improved thermostability, the weathering resistance of product.

In the comparing embodiment, do not add discoloring agent, oxidation inhibitor, the color that obtains product is darker, is No. 3 (Ghana's look number).Do not add thermo-stabilizer, photostabilizer, so the color after the heat stability test of product is No. 6 (Ghana's look number); Rate of body weight gain after the weather resisteant test is 1.60%, and color increases by 4 Ghana's looks number.And the product that the present invention obtains, the Ha Sense of color number less than No. 150 (less than 1 Ghana's look number); Colour-change after the heat stability test is not more than 1 Ghana's look number; Rate of body weight gain after the weather resisteant test is not more than 0.2%, and colour-change is not more than 3 Ghana's looks number.

Four. embodiment

Embodiment 1

A kind of high stability color-less rosin pentaerythrite ester, the Ha Sense of this color of resin number less than No. 150; Heat stability is good: place 8h in 180 ℃ of air dry ovens, colour-change is not more than 1 Ghana's look number; Weather resisteant is good: under 20 ℃, apart from the following irradiation 15h of 500W ultraviolet lamp 50cm, rate of body weight gain is not more than 0.2%, and colour-change is not more than 3 Ghana's looks number.

Embodiment 2

In second step, under inert atmosphere conditions, inert atmosphere can be N ₂, Ar, He, CO ₂Etc. atmosphere, in resin, add tetramethylolmethane and the discoloring agent that accounts for resin quality 0.1～1.0%, the anthraquinone that accounts for resin quality 0.01～0.1% that accounts for resin quality 11.0～16.0%, the catalyzer that accounts for resin quality 0.1～0.5% as oxidation inhibitor, under 230～290 ℃, carry out esterification, reacted 3-10 hour, and reacted to acid number and finish less than 20mg/g; Wherein, discoloring agent is 4,4-thiobis-(6-tertiary butyl meta-cresol) or 4,6-pair-(dodecyl sulfo-)-ortho-cresol or nonyl phenol two sulphur oligopolymer (as The mixture of one or more n=0,1,2), the proportioning of mixture can be any proportioning; Catalyzer is that ZnO or Mgo or sterically hindered phenol phosphate compounds are (as two [ethyl (3,5-di-t-butyl-4 acrinyl phosphoric acid)] calcium salt, two [ethyl (3,5-di-t-butyl-4 acrinyl phosphoric acid)] zinc salt) the one or more kinds of mixtures in, the proportioning of mixture can be any proportioning, and wherein, the ratio that tetramethylolmethane accounts for resin can be 11.5%, 12.4%, 13.2%, 14.6%, 15.7%, the ratio that discoloring agent accounts for resin can be 0.2%, 0.4%, 0.7%, 0.9%, the ratio that anthraquinone accounts for the resin quality can be 0.03%, 0.04%, 0.07%, 0.08%, 0.09%, esterification reaction temperature can be 235 ℃, 242 ℃, and 256 ℃, 268 ℃, 275 ℃, 284 ℃

In the 3rd step, with the decompression of above-mentioned reaction product atmosphere of living in, and to keep vacuum tightness be 0～2kPa, and the hold-time is 0.5～2 hour, to remove low boilers (neutrals in water, unreacted tetramethylolmethane or the resin that generates during as esterification); Wherein vacuum tightness can be 0.3kPa, 0.8kPa, and 1.5kPa, the hold-time can be 0.8 hour, 1.8 hours

The 4th step, the reaction product of removing low boilers is cooled to 200～230 ℃, for example can be 210 ℃, 220 ℃, 224 ℃, add the thermo-stabilizer account for resin quality 0.1～1.0% and account for the photostabilizer of resin quality 0.1～1.0% and stir, obtain high stability color-less rosin pentaerythrite ester; Wherein, thermo-stabilizer is 2,5-ditert-butylhydro quinone or 2,6-di-tert-butyl-4-methy phenol or tricresyl phosphite (nonyl phenyl ester) or three (2, the 4-di-tert-butyl-phenyl) the one or more kinds of mixtures in phosphorous acid ester or the triphenyl phosphite, the proportioning of mixture can be any proportioning, photostabilizer is Succinic Acid and (4-hydroxyl-2,2,6,6-tetramethyl--1-sends pyridine alcohol) polymkeric substance or one or more the mixture in 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole or the Octabenzone, the proportioning of mixture can be any proportioning, in the present embodiment, thermo-stabilizer accounts for the resin mass percent can 0.3%, 0.5%, 0.6%, 0.8%, photostabilizer accounts for the resin mass percent can be 0.2%, 0.4%, 0.5%, 0.7%.

Among the present invention, discoloring agent, oxidation inhibitor, catalyzer can add a collection of or in batches.

In the present embodiment, esterification reaction temperature is preferably 270～285 ℃, corresponding 5～8 hours reaction times; The per-cent that tetramethylolmethane accounts for the resin quality is preferably 12.4～14.0%; The per-cent that discoloring agent accounts for the resin quality is preferably 0.2～0.5%; The per-cent that oxidation inhibitor accounts for the resin quality is preferably 0.02～0.05%; The per-cent that catalyzer accounts for the resin quality is preferably 0.2～0.4%; The per-cent that thermo-stabilizer accounts for the resin quality is preferably 0.2～0.4%; The per-cent that photostabilizer accounts for the resin quality is preferably 0.2～0.4%.

Embodiment 3

1000g resin, 140g tetramethylolmethane and 2g 300,0.2g anthraquinone, 3g ZnO are added reaction flask, feed N ₂, be heated to 280 ± 2 ℃, react to acid number less than 20mg/g, decompression, keep vacuum tightness be 0～0.6kPa to there not being overhead product, be cooled to 220 ℃, add 1g 2,6 di tert butyl 4 methyl phenol, 1g tricresyl phosphite (nonyl phenyl ester) and 1g Octabenzone.

Product in the present embodiment (color-less rosin pentaerythrite ester 1) color: 150 (Ha Sense numbers), acid number: 14.2mg/g, softening temperature: 105.1 ℃, heat stability test (180 ℃, 8h): color, 200 (Ha Sense numbers); Weather resisteant test: rate of body weight gain, 0.20%, color increases by 3 Ghana's looks number.

Embodiment 4

1000g resin, 124g tetramethylolmethane and 1g 300,0.1g anthraquinone, 2g ZnO are added reaction flask, feed N ₂Be heated to 280 ± 2 ℃, reaction 3h, add 1g 300,0.1g anthraquinone, 1g ZnO remain on 280 ± 2 ℃ react to acid number less than 20mg/g, decompression, keep vacuum tightness be 0～0.6kPa to there not being overhead product, be cooled to 220 ℃, add 1g 2,6 di tert butyl 4 methyl phenol, 1g tricresyl phosphite (nonyl phenyl ester), 1g Octabenzone.

Product in the present embodiment (color-less rosin pentaerythrite ester 2) color: 100 (breathing out gloomy), acid number: 19.8mg/g, softening temperature: 103.0 ℃, heat stability test (180 ℃, 8h): color, 150 (breathing out gloomy); Weather resisteant test: rate of body weight gain, 0.19%, color increases by 3 Ghana's looks number.

Embodiment 5

1000g resin, 150g tetramethylolmethane and 2g 300,0.2g anthraquinone, 2g ZnO are added reaction flask, feed N ₂Be heated to 280 ± 2 ℃, reaction 3h, add 2g 300,0.2g anthraquinone, 2g ZnO remain on 280 ± 2 ℃ react to acid number less than 20mg/g, decompression, keep vacuum tightness be 0～0.6kPa to there not being overhead product, be cooled to 220 ℃, add 2g 2,6 di tert butyl 4 methyl phenol, 2g tricresyl phosphite (nonyl phenyl ester), 2g Octabenzone.

Product in the present embodiment (color-less rosin pentaerythrite ester 3) color: 100 (breathing out gloomy), acid number: 15.2mg/g, softening temperature: 107.1 ℃, heat stability test (180 ℃, 8h): color, 125 (breathing out gloomy); Weather resisteant test: rate of body weight gain, 0.15%, color increases by 3 Ghana's looks number.

Comparing embodiment

1000g resin, 124g tetramethylolmethane and 2g ZnO are added reaction flask, feed N ₂, be heated to 280 ± 2 ℃, remain on 280 ± 2 ℃ react to acid number less than 20mg/g, decompression, keep vacuum tightness be 0～0.6kPa to there not being overhead product, be cooled to 220 ℃, discharging.

Product in the present embodiment (resin pentaerythritol ester 1) color: 3 (Ghana's looks number), acid number: 19.8mg/g, softening temperature: 104.0 ℃, heat stability test (180 ℃, 8h): color, 6 (Ghana's looks number); Weather resisteant test: rate of body weight gain, 1.60%, color increases by 4 Ghana's looks number.

Claims

1. A colorless pentaerythritol ester of colorless rosin with high stability, characterized in that the Hasson color number of the resin color is less than No. 150; thermal stability: placed in a blast drying oven at 180°C for 8 hours, the color change is not more than 1 Garner color No.: Weather resistance: at 20°C, irradiated for 15 hours at a distance of 50cm from a 500W ultraviolet lamp, the weight gain rate is not more than 0.2%, and the color change is not more than 3 Ghanaian color numbers.

2. a preparation method of high stability colorless rosin pentaerythritol ester according to claim 1, is characterized in that comprising the steps:

In the first step, the super-grade rosin is distilled at a vacuum degree of 0-1kPa and a temperature of 180-270°C. The color of the prepared color is no greater than No. 3 in Ghana, the acid value is 160mg/g-190mg/g, and the softening point is 70°C ~85℃ refined rosin;

In the second step, under the protection of an inert atmosphere, add pentaerythritol accounting for 11.0 to 16.0% of the mass of refined rosin and a decolorizer accounting for 0.1 to 1.0% of the mass of refined rosin and 0.01 to 0.1% of the mass of refined rosin as an antioxidant to the refined rosin. Anthraquinone as an additive and a catalyst accounting for 0.1-0.5% of the mass of refined rosin are subjected to an esterification reaction at 230-290°C until the acid value is less than 20 mg/g; among them, the decolorizing agent is 4,4-thiobis - one or more mixtures of (6-tert-butyl-m-cresol) or 4,6-bis-(dodecylthio)-o-cresol or nonylphenol disulfide oligomers, The ratio of the mixture can be any ratio; the catalyst is one or a mixture of two or more of ZnO, Mgo or hindered phenol phosphate compounds, and the ratio of the mixture can be any ratio;

The third step is to depressurize the atmosphere where the above reaction product is located, and maintain a vacuum degree of 0-2kPa for 0.5-2h to remove low boiling point substances;

In the fourth step, the temperature of the reaction product from which low boiling point substances have been removed is lowered to 200-230° C., a heat stabilizer accounting for 0.1-1.0% of the mass of refined rosin and a light stabilizer accounting for 0.1-1.0% of the mass of refined rosin are added and stirred evenly to obtain High stability colorless rosin pentaerythritol ester; among them, heat stabilizer is 2,5-di-tert-butyl hydroquinone or 2,6-di-tert-butyl-4-methylphenol or tris(nonylbenzene phosphite ester) or three (2,4-di-tert-butylphenyl) phosphite or one or more mixtures of triphenyl phosphite, the mixture ratio can be any ratio, the light stabilizer is Polymer of succinic acid with (4-hydroxy-2,2,6,6-tetramethyl-1-pyridinol) or 2-(2'-hydroxy-3'-tert-butyl-5'-methanol phenyl)-5-chlorobenzotriazole or 2-hydroxyl-4-n-octyloxybenzophenone or a mixture of two or more, and the proportion of the mixture can be any proportion.

3. the preparation method of high-stability colorless rosin pentaerythritol ester according to claim 2 is characterized in that the esterification reaction temperature is 270～285 ℃, and the reaction time is 5～8 hours.

4. the preparation method of high-stability colorless rosin pentaerythritol ester according to claim 2 is characterized in that the percentage that pentaerythritol accounts for refined rosin quality is 12.4～14.0%.

5. the preparation method of high-stability colorless rosin pentaerythritol ester according to claim 2 is characterized in that the percentage that decolorizing agent accounts for refined rosin quality is 0.2～0.5%.

6. the preparation method of high-stability colorless rosin pentaerythritol ester according to claim 2, is characterized in that the percentage that antioxidant accounts for refined rosin quality is 0.02～0.05%.

7. the preparation method of high-stability colorless rosin pentaerythritol ester according to claim 2 is characterized in that the percentage that catalyst accounts for refined rosin quality is 0.2～0.4%.

8. The preparation method of the highly stable colorless rosin pentaerythritol ester according to claim 2, characterized in that the heat stabilizer accounts for 0.2 to 0.4% of the mass of the refined rosin.

9. The preparation method of the highly stable colorless rosin pentaerythritol ester according to claim 2, characterized in that the light stabilizer accounts for 0.2 to 0.4% of the mass of the refined rosin.