CN103819640A - Method for preparing acrylic acid modified rosin phenolic resin - Google Patents

Abstract

The invention provides a method for preparing acrylic acid modified rosin phenolic resin. The molar ratio of rosin, acrylic acid, maleic anhydride, bisphenol, methanal, pentaerythritol to yttrium oxide is 1:0.2:0.3:0.2:0.3:0.3:0.1, and the method includes the following steps: heating rosin at the temperature of 180-200 DEG C; adding maleic anhydride, and reacting for 1.5-2 h at the temperature of 180-200 DEG C; adding yttrium oxide, and reacting for 80-90 min at the temperature of 250-260 DEG C; dropwise adding acrylic acid and controlling the adding speed to the extent that all the acrylic acid is added dropwise within 45-50 min; adding bisphenol A and stirring for 0.3-0.5 h; adding methanal and stirring for 2-2.5 h at the temperature of 90-100 DEG C; adding pentaerythritol and heating to 180-200 DEG C and reacting for 2-2.5 h; vacuumizing for 1 h at the temperature of 270-280 DEG C to obtain the product. The method has the advantages that the design is scientific and reasonable, the reaction speed is high and gentle, control is easy, the product is light in color and good in quality, and has the softening point reaching 185 DEG C above, and the production cost is reduced.

Description

Acrylic acid modified rosin yttrium preparation method of phenolic resin

Technical field

The invention belongs to a kind of rosin deep processing method.

Background technology

Rosin is the renewable resources of China's abundant, and annual production reaches more than 60 ten thousand tons, ranks first in the world.It has unique chemical structure and mulitiple chiral centers by a series of resin acid compositions, and the carboxyl in structure and phenanthrene ring frame can carry out a series of chemical modification, is a kind of natural chiral source material.Rosin can obtain a series of deep processed products through chemical modification, is widely used in the every field in daily life, plays very important effect in the national economic development.The value ratio raw material rosin of these deep processed products is mentioned 2-10 doubly, even decades of times, and China mainly earns foreign exchange with outlet gum resin at present.China is the country of gum resin export volume maximum, accounts for 60% left and right of volume of world trade, and many developed countries are from China's imported raw material rosin, and after a series of deep processings, product is exported go back to again China back, and the conservation of resources to China and Economic development are very unfavorable.China is 35% to rosin deep processing and utilization rate, and by contrast, the developed countries such as America and Europe approach 100% to the deep processing and utilization rate of rosin, exist very large gap.Therefore, carry out Abietyl modified research, develop the not only development to country and local economy of deep processing rosin product that meets China market demand, and reasonable development to China's forest resourceies and utilization and at present industrial energy saving lower consumption and be all of great significance.That one has two chemical reactivity centers as the resinous acid of rosin main component---the chemically reactive substance of carboxylic acid and two keys, just can introduce atom or group at quarter by these two chain carriers, thereby give rosin and there is desirable character, reach the object of modification, thereby change the rational performance of rosin, greatly expand the Application Areas of rosin, formed miscellaneous rosin derived product, be widely used in pressure sensitive adhesive, tackiness agent industry.Manufacture multiple film glue, decorating glue, label glue, adhesive tape glue, hot melt adhesive, sanitary towel glue, non-setting adhesive, EVA hot melt adhesive, polyamide hot, seal gum, varnish paint vehicle, bookbinding glue, pipeline glue etc.In recent decades, rosin deep processing aspect, its product category, preparation method are all without large progress; , there is the deficiencies such as sluggish length consuming time in prior art products preparation method.

Through Chinese publication retrieval, find 527 of relevant patents of invention, do not find the scheme identical with present patent application.

Summary of the invention

The object of the invention is to: for the deficiencies in the prior art, propose a kind of acrylic acid modified rosin yttrium preparation method of phenolic resin.

Acrylic acid modified rosin yttrium preparation method of phenolic resin of the present invention, is characterized in that: material ratio is, rosin: vinylformic acid: MALEIC ANHYDRIDE: bis-phenol: formaldehyde: tetramethylolmethane: the mol ratio of yttrium oxide is 1:0.2:0.3:0.2:0.3:0.3:0.1; Its technique comprises the following steps, and by proportioning quantity, by rosin heating and melting under rare gas element, heats up 180-200 ℃, adds MALEIC ANHYDRIDE, reacts 1.5-2 hours at 180-200 ℃; Add yttrium oxide, be warming up to 250-260 ℃ of reactions 80-90 minutes, then, control the speed dropping vinylformic acid adding with 45-50 minutes, add dihydroxyphenyl propane, stir 0.3-0.5 hour, be cooled to 90-100 ℃, add formaldehyde, 90-100 ℃ are stirred 2-2.5 hours, add tetramethylolmethane, heat up 180-200 ℃, stirring reaction 2-2.5 hours, is warming up to 270-280 ℃ and vacuumizes 1 hour; Both obtained product.

Product of the present invention has lighter color, and softening temperature high is applied to the industrial sectors such as paint, ink, synthetic resins, tackiness agent, electronics, chemical industry.

The present invention's beneficial effect compared with prior art: design science is reasonable, speed of response is fast and relax, and is easy to control, and product look shallow, softening temperature is above up to 185 ℃, quality is good, the advantages such as production cost reduction.

Embodiment

The raw materials used acquisition of buying of the present invention.

Acrylic acid modified rosin yttrium preparation method of phenolic resin of the present invention, is characterized in that: material ratio is, rosin: vinylformic acid: MALEIC ANHYDRIDE: bis-phenol: formaldehyde: tetramethylolmethane: the mol ratio of yttrium oxide is 1:0.2:0.3:0.2:0.3:0.3:0.1; Its technique comprises the following steps, and by proportioning quantity, by rosin heating and melting under rare gas element, heats up 180-200 ℃, adds MALEIC ANHYDRIDE, reacts 1.5-2 hours at 180-200 ℃; Add yttrium oxide, be warming up to 250-260 ℃ of reactions 80-90 minutes, then, control the speed dropping vinylformic acid adding with 45-50 minutes, add dihydroxyphenyl propane, stir 0.3-0.5 hour, be cooled to 90-100 ℃, add formaldehyde, 90-100 ℃ are stirred 2-2.5 hours, add tetramethylolmethane, heat up 180-200 ℃, stirring reaction 2-2.5 hours, is warming up to 270-280 ℃ and vacuumizes 1 hour; Both obtained product.

Products obtained therefrom quality index reaches following index:

Claims (1)

1. an acrylic acid modified rosin yttrium preparation method of phenolic resin, is characterized in that: material ratio is, rosin: vinylformic acid: MALEIC ANHYDRIDE: bis-phenol: formaldehyde: tetramethylolmethane: the mol ratio of yttrium oxide is 1:0.2:0.3:0.2:0.3:0.3:0.1; Its technique comprises the following steps, and by proportioning quantity, by rosin heating and melting under rare gas element, heats up 180-200 ℃, adds MALEIC ANHYDRIDE, reacts 1.5-2 hours at 180-200 ℃; Add yttrium oxide, be warming up to 250-260 ℃ of reactions 80-90 minutes, then, control the speed dropping vinylformic acid adding with 45-50 minutes, add dihydroxyphenyl propane, stir 0.3-0.5 hour, be cooled to 90-100 ℃, add formaldehyde, 90-100 ℃ are stirred 2-2.5 hours, add tetramethylolmethane, heat up 180-200 ℃, stirring reaction 2-2.5 hours, is warming up to 270-280 ℃ and vacuumizes 1 hour; Both obtained product.