CN104744725A - Cardanol modified plasticizer and preparation method thereof - Google Patents

Abstract

The invention provides a cardanol modified plasticizer of which the structural formula is disclosed in the specification. The invention also provides a preparation method of the cardanol modified plasticizer, which comprises the following steps: hydrogenating cardanol to obtain saturated alkyl cardanol, and esterifying the saturated cardanol to obtain the saturated alkyl cardanol carboxylate. The bio-based plasticizer product synthesized from the cardanol and various acid anhydrides has excellent plasticity, can substitute the orthophthalic plasticizer, is green and environment-friendly, can effectively improve the compatibility, heat resistance, weather resistance, electric conductivity and other physical properties of polymers, and has wide development prospects.

Description

A kind of modified by cardanol softening agent and preparation method thereof

Technical field:

The invention belongs to chemical field, particularly relate to a kind of modified by cardanol compound, specifically a kind of modified by cardanol softening agent and preparation method thereof.

Background technology:

Current global softening agent annual production is 8,000,000 tons, and wherein Chinese output has more than 450 ten thousand tons, accounts for 56% of global annual production.China's softening agent year consumption is 220 tons, accounts for 37% of global consumption, year nearly 110,000 tons of import volume.China is the maximum plasticizer production state in the whole world, country of consumption and importer.Conventional plasticizers phthalate large usage quantity, accounts for 88% of the softening agent market share, but but finds that phthalic ester has persistent genotoxicity in the application.Seeking adjacent benzene class softening agent substitute that is nontoxic, environmental protection has been the focus of global concern.Bio-based softening agent is raw material with natural reproducible resource, has the features such as biodegradable, nontoxic, raw material is renewable, and has shock absorption to the energy dilemma of increasingly sharpening, have huge economic results in society and development prospect.Cashew nut shell oil is the agriculture byproduct in the global the third-largest agricultural exports cashew nut course of processing, cheap, abundance.Cardanol extract from cashew nut shell oil, and unique chemical structure makes it can replace multiple phenols petrochemical material, is applied to the fields such as polymer chemistry synthetic materials, tamanori, coating, matrix material.

CN103342834A, discloses a kind of Epoxy anacardol acetic acid ester plasticizer and preparation method thereof, and it utilizes hydrogen peroxide unsaturated for cardanol phenol long-chain process for epoxidation, overcomes product variable color and rotten in storage process." chemistry of forest product with industry ", the synthesis of 2013,5:45-49. cardanol yl acetate and plasticising performance study thereof, near the plasticising performance can finding out cardanol acetic ester, phthalate anhydride class softening agent is better.

Summary of the invention:

The object of the present invention is to provide a kind of modified by cardanol softening agent and preparation method thereof, described this modified by cardanol softening agent and preparation method thereof solves plasticizer phthalic acid ester class of the prior art to be had persistent genotoxicity, affects the technical problem of human health.

The invention provides a kind of modified by cardanol softening agent, its structural formula is: wherein R is methyl, ethyl, propyl group, sec.-propyl, normal-butyl or the tertiary butyl.

Present invention also offers the preparation method of above-mentioned a kind of modified by cardanol softening agent, comprise the steps:

1) step of pentadecyl cardanol is prepared for one, cardanol and propyl carbinol is added in autoclave, wherein propyl carbinol is as solvent, described cardanol and the mass ratio of propyl carbinol are 1:3 ~ 4, add Raney's nickel and pass into hydrogen and start to react, the mass ratio of Raney's nickel and cardanol is 0.8 ~ 1.5:200, temperature of reaction is 80 ~ 100 degree, reaction times is 3 ~ 6 hours, nitrogen pressure table power 3 ~ 6MPa, the cardanol after hydrogenation is obtained through separating-purifying, i.e. pentadecyl cardanol after reaction terminates;

2) in pentadecyl cardanol, acid anhydrides is added, the mol ratio of described acid anhydrides and pentadecyl cardanol is 1 ~ 1.5:1, add NaOH, described NaOH and the mass ratio of cardanol are 0.8 ~ 1.5:200, be under the condition of catalyzer at NaOH, be warmed up to 60 ~ 70 degree, react 4 ~ 5h at this temperature, then at this temperature, vacuumize 3 ~ 4h, standing separation obtains modified by cardanol softening agent.

Reaction process of the present invention describes as follows:

Further, described acid anhydrides is diacetyl oxide or isobutyric anhydride.

The present invention, by by cardanol hydrogenation, obtains saturated alkyl cardanol, then by saturated cardanol esterification, obtains saturated alkyl cardanol carboxylicesters.

The present invention for Material synthesis softening agent with the cardanol of cheap environmental protection, utilizes hydrogenation to make the unsaturated long-chain of cardanol become saturated, increases the stability of product, the hydrogenation raney ni catalysis of cardanol, safe and reliable, esterification uses NaOH to make catalyzer, economical and practical.

The present invention compares with prior art, and its effect is actively with obvious.The present invention with cardanol and various acid anhydrides for Material synthesis bio-based softening agent, its product plasticising excellent performance, adjacent benzene class softening agent can not only be replaced, environmental protection, and effectively can improve the physicals such as consistency and heat-resisting, weather-proof, electroconductibility of polymkeric substance, there is vast potential for future development.

Embodiment:

Embodiment 1:

1. in autoclave, add 300g cardanol and 1000g propyl carbinol, wherein propyl carbinol is as solvent, add 1.5g Raney's nickel and pass into hydrogen and start to react, temperature of reaction is 100 degrees Celsius, reaction times is 4 hours, nitrogen pressure table is 4MPa, obtains the cardanol after hydrogenation through separating-purifying, i.e. pentadecyl cardanol.

2. get the cardanol 305g after hydrogenation, the NaOH solid of diacetyl oxide 112g and 1.5g adds reactor, at 60 DEG C, react 4h, then at this temperature, vacuumizes 4h, and standing separation obtains the finished product modified by cardanol softening agent.

3. research is 4:1 at epoxy resin E51/ solidifying agent T31 mass ratio, cardanol yl acetate add-on is 10%, solidification value is 25 degrees Celsius, and set time is under the condition of 7 days, and different softening agent is on the impact of epoxy resin E51/ solidifying agent T31 curing system mechanical property.

The different softening agent of table 1 is to the Effect on Mechanical Properties of E51/T31 curing system

Softening agent	Hardness	Elongation at break	Snappiness	Shock strength
					Nothing	4H	0.54％	3 grades	30cm
Cardanol yl acetate	3H	3.54％	1 grade	50cm
					Dioctyl phthalate (DOP)	3H	1.02％	2 grades	35cm
Dioctyl terephthalate	3H	2.11％	1 grade	40cm

Cardanol yl acetate has great improvement to the snappiness of E51/T31 curing system and intensity as can be seen from Table 1.

Embodiment 2:

1. in autoclave, add 300g cardanol and 1000g propyl carbinol, wherein propyl carbinol is as solvent, add 1.5g Raney's nickel and pass into hydrogen and start to react, temperature of reaction is 100 degrees Celsius, reaction times is 4 hours, nitrogen pressure table is 4MPa, obtains the cardanol after hydrogenation through separating-purifying, i.e. pentadecyl cardanol.

2. get the cardanol 305g after hydrogenation, the NaOH solid of isobutyric anhydride 186g and 1.5g adds reactor, at 60 DEG C, react 4h, then at this temperature, vacuumizes 4h, and standing separation obtains the finished product modified by cardanol softening agent.

3. research is 4:1 at epoxy resin E51/ solidifying agent T31 mass ratio, cashew nut phenolic group butyric ester add-on is 10%, solidification value is 25 degrees Celsius, and set time is under the condition of 7 days, and different softening agent is on the impact of epoxy resin E51/ solidifying agent T31 curing system mechanical property.

The different softening agent of table 2 is to the Effect on Mechanical Properties of E51/T31 curing system

Softening agent	Hardness	Elongation at break	Snappiness	Shock strength
					Nothing	4H	0.54％	3 grades	30cm
Cashew nut phenolic group butyric ester	2H	3.84％	1 grade	50cm
					Dioctyl phthalate (DOP)	3H	1.02％	2 grades	35cm
Dioctyl terephthalate	3H	2.11％	1 grade	40cm

Cashew nut phenolic group butyric ester also has outstanding performance and has larger elongation at break than cardanol acetic ester as can be seen from Table 2, although hardness decreases, degree is little, meets the use under most of occasion completely.To sum up two examples can find out that cardanol yl carboxylic acid ester can give the mechanical property of epoxy resin excellence.

Claims (3)

1. a modified by cardanol softening agent, is characterized in that its structural formula is: wherein R is methyl, ethyl, propyl group, sec.-propyl, normal-butyl or the tertiary butyl.

2. the preparation method of a kind of modified by cardanol softening agent according to claim 1, is characterized in that comprising the steps:

1) step of pentadecyl cardanol is prepared for one, cardanol and propyl carbinol is added in autoclave, wherein propyl carbinol is as solvent, described cardanol and the mass ratio of propyl carbinol are 1:3 ~ 4, add Raney's nickel and pass into hydrogen and start to react, the mass ratio of Raney's nickel and cardanol is 0.8 ~ 1.5:200, temperature of reaction is 80 ~ 100 degree, reaction times is 3 ~ 6 hours, nitrogen pressure table power 3 ~ 6MPa, the cardanol after hydrogenation is obtained through separating-purifying, i.e. pentadecyl cardanol after reaction terminates;

2) in pentadecyl cardanol, acid anhydrides is added, the mol ratio of described acid anhydrides and pentadecyl cardanol is 1 ~ 1.5:1, add NaOH, described NaOH and the mass ratio of cardanol are 0.8 ~ 1.5:200, be under the condition of catalyzer at NaOH, be warmed up to 60 ~ 70 degree, react 4 ~ 5h at this temperature, then at this temperature, vacuumize 3 ~ 4h, standing separation obtains modified by cardanol softening agent.

3. the preparation method of a kind of modified by cardanol softening agent according to claim 1, is characterized in that: described acid anhydrides is diacetyl oxide or isobutyric anhydride.