CN101525419B - Polyester made of raw material of 1,2-propylene glycol - Google Patents

Abstract

The invention discloses a polyester made of a raw material of 1,2-propylene glycol. The polyester is characterized in that the polyester is a macromolecular polyester prepared by the reaction of aromatic dicarboxylic acid or derivatives of the aromatic dicarboxylic acid and 1,2-propylene glycol, wherein the carbon element in the 1,2-propylene glycol is biologically sourced. The polyester has the advantages of releasing the tension of petroleum resources, reducing the emission of CO2 and further protecting the environment.

Description

Adopt 1, the polyester of 2-Ucar 35 raw material

Technical field:

The present invention relates to the raw-material polyester of a kind of use biogenetic derivation.

Technical background:

Along with current industrial development, also increasing to the demand of polyester material, and the raw material of polyester all is to derive from petroleum resources basically, this will cause the madness of oil price to go up undoubtedly again; A large amount of waste polyesters has brought very big pressure to environment simultaneously, and white pollution has become one of the most important environmental problem in the present age.Therefore, the pursuit of environmentally friendly material and the exploitation of biogenetic derivation material become the important means that many companies occupy the first market opportunities.

People use reproducible Biological resources; Various novel polyester have been developed; For example E.I.Du Pont Company through biology and chemical process, prepares 1 through corn is fermented; 3-PDO, and developed and contain that the 36wt% that has an appointment derives from biomaterial but not PTT (PTT) polymkeric substance of oil material.Natureworks company is raw material equally with farm crop, through biology and chemical process, has produced pure biogenetic derivation and has been easy to biodegradable POLYACTIC ACID (PLA) polymkeric substance.Also there are a lot of units to utilize farm crop to make multicomponent binary alcohol at home; Then multi-component divalent alcohol is separated and make highly purified various divalent alcohol; It is cheap and be reproducible that this method is made the raw material of divalent alcohol, compares to utilize petroleum resources to make the polyester raw material divalent alcohol to have more wide prospect.

Farm crop are a kind of renewable resourcess, can be converted into various starch, carbohydrate, Mierocrystalline cellulose, xylogen etc. and in farm crop fruit and stalk thereof, store with airborne CO2 through photosynthesis.

Summary of the invention:

The object of the present invention is to provide a kind of employing 1 that meets the environmental protection needs, the polyester of 2-Ucar 35 raw material.

Technical solution of the present invention is:

A kind of employing 1, the polyester of 2-Ucar 35 raw material is characterized in that: be by aromatic dicarboxylic acid or derivatives thereof and 1, the macromolecule polyester that the 2-Ucar 35 obtains through reaction, wherein 1, carbon derives from biomaterial in the 2-Ucar 35.

Biomaterial is the stalk of corn, sugarcane, wheat or other farm crop.Wherein corn, wheat are its seed and/or stalk.

Through biomaterial production obtain 1, in the 2-Ucar 35,1, the 2-content of propylene glycol is between 95%-99.9%, and the light transmission rate in wavelength is 190～350nm scope is more than 50%.

Also contain carbon in the polyester and derive from the diprotic acid of petroleum and the copolymer composition of divalent alcohol.

Said aromatic dicarboxylic acid or derivatives thereof is terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate.

The limiting viscosity of polyester is 0.50-0.95.

The present invention utilizes the stalk of corn, wheat, sugarcane and other farm crop, and the process biological fermentation and/or the chemical industry course of processing make the raw material 1 of poly terephthalic acid 1,2 propylene glycol ester, 2-Ucar 35.Obtain 1, the 2-Ucar 35 through biology and/or chemical process.For example corn is through the bioprocess separating starch, and through processing the sugar that obtains 5 carbon and 6 carbon, these sugars can be prepared multicomponent binary alcohol through the technology of hydrogenation catalysts; Through after the purifies and separates general procedure, again to separation obtain 1, the 2-Ucar 35 carries out heat treated; Wherein the temperature of heating is 150～200 ℃, and the time of heating is 2～10 hours, contacts processing after cooling again with gac; Just can obtain raw material divalent alcohol 1 of the present invention, 2-Ucar 35 component.In the product 1, the carbon of 2-Ucar 35 derives from biological raw material.

Use among the present invention 1, the 2-Ucar 35 can contain other glycol component such as terepthaloyl moietie, 1,4-butyleneglycol, 1.2 pentanediols, other divalent alcohol such as 2,3 butyleneglycols.

Poly terephthalic acid 1 among the present invention, the 2-propylene glycol ester is obtained by diacid and glycol reaction, and wherein diacid is the verivate of terephthalic acid and esterification thereof, can be terephthalic acid, DMT. Dimethyl p-benzenedicarboxylate, diethyl terephthalate etc.

Among the present invention, poly terephthalic acid 1,2-propylene glycol ester are through being obtained by diacid and glycol reaction.Wherein diacid is the verivate of terephthalic acid and esterification thereof, can be terephthalic acid, DMT. Dimethyl p-benzenedicarboxylate, diethyl terephthalate etc.Diacid unit further among the present invention contains m-phthalic acid; M-phthalic acid-5-sulphonate; Phthalic acid; The methyl terephthalic acid; The naphthalene diacid; The aryl dicarboxylic acid's class and the Succinic Acid of aromatic carboxylic acids such as biphenyl dicarboxylic acid and ester derivative thereof; Hexanodioic acid; Pimelic acid; Suberic acid; Nonane diacid; Aliphatic carboxylic acid and ester derivative and cyclohexane dicarboxylic acids such as dodecanedicarboxylic acid; The hexahydro-m-phthalic acid; Alicyclic dicarboxylic acid and ester derivatives thereof such as hexahydro-phthalic acid.Be meant materials such as lower alkyl esters, acid anhydrides, acyl chlorides such as dimethyl ester in the described verivate.These dicarboxylicacid can two or more alone or in combination uses.

The carbon that poly terephthalic acid 1 among the present invention, 2-propylene glycol ester can also contain other derives from the diprotic acid of oil and the copolymer composition of divalent alcohol.Glycol component can be exemplified as: carbon numbers such as pinakon, Ucar 35, butyleneglycol, pentanediol are the saturated and unsaturated divalent alcohol of 2-30; High-molecular weight divalent alcohol such as polyoxyethylene glycol, W 166, polytetramethylene glycol.

Poly terephthalic acid 1 of the present invention; 2 propylene glycol esters can pass through existing apparatus and process; At first through esterification or transesterification reaction; In this process, can use known catalyzer, can enumerate by one or more mixture in tetrabutyl titanate, isopropyl titanate, n-butylstannoic acid, manganese acetate, Cobaltous diacetate, the magnesium acetate.It is 95% or 95% above the time that esterification or transesterification reaction reach reactivity; Polycondensation is carried out in transfer; The used catalyzer of polycondensation is a metal titanium class catalyzer; Titanium compound is for having the structure of; Wherein R1, R2, R3, R4 are alkyl, the alkyl of unsaturated carbon, hydroxyalkyl, the acetylize alkyl of saturated carbon, and wherein R1, R2, R3, R4 can be identical groups, also can be different moiety combinations.Specifically can be tetrabutyl titanate, sec.-propyl titanic acid ester, propyl group titanic acid ester, propenyl titanic acid ester.

Can add various stablizer phosphorus compounds commonly used among the present invention; Be trivalent or phosphoric organic or inorganic compound; That can simply enumerate has phosphoric acid, trimethyl phosphite 99, a triphenylphosphate; Can be the trivalent of commercially available phosphorus system and the inhibitor of pentavalent, like commercially available PEP36, AP1500, AX-71.Do not enumerate more specifically at this.

Polycondensation is carried out under 200 ℃ of-280 ℃ of conditions in temperature, reaches polycondensation under 200 pascals and the following vacuum condition gradually, deviates from the small molecules glycol; When the viscosity of polymkeric substance is in the 0.50-0.95 scope; Can finish reaction, obtain poly terephthalic acid 1 of the present invention, the 2-propylene glycol ester.

Poly terephthalic acid 1,2 propylene glycol ester of the present invention can use the polymerization of still formula, the semi-continuous polymerzation of discontinuous, the method for successive polymerization to produce.

The poly terephthalic acid 1 that the present invention obtains, the 2-propylene glycol ester can utilize POY spinning equipment, DTY in the existing polyester industrial to add bullet equipment, Weaving device and dyeing installation, carries out high speed spinning, adds bullet, weaves and dye.Poly terephthalic acid 1,2 propylene glycol ester can be used in various fields such as resin, film, fiber among the present invention, processes various subsequent products, and it has than better dyeing behavior of common PET and flowability.

Embodiment:

Biogenetic derivation 1, the 2-Ucar 35: great achievement group in Changchun produces, and the carbon source is corn; Purity: 97%; Pass through heat treated then, handle with the gac contact again, handle the biology 1 that obtains; The light transmission rate of 2-Ucar 35 when ultraviolet region 250nm is 65%, and the light transmission rate during 300nm is 90%.

1, and the 2-Ucar 35 (1,2-PDO): Shanghai hat dagger-axe Industrial Co., Ltd., analytical pure.

Terephthalic acid (PTA): sub-petrochemical iy produced, polymerization-grade are raised by China.

DMT. Dimethyl p-benzenedicarboxylate (DMT): Iranian Fiber Intermediate Products Co. produces

Embodiment 1:

Esterification: with the PTA of 2Kg and the biogenetic derivation 1 of 1053g, 2-PDO is mixed and made into slurry, drops in 4 mouthfuls of flasks of the 4L that has the electronics stirring, adds the butyl stannonic acid of 1.12g and the tetrabutyl titanate of 1.20g; Temperature is raised to 200～250 ℃, and stirring velocity is transferred to 200r/m and is carried out esterification and collect water byproduct, calculates according to aquifer yield, when reactivity stopped reaction greater than 95% time; Product is spued in dull and stereotyped pallet.

Polycondensation: take by weighing the product 317g of esterification, putting into diameter is in the hard Boiling tube of 80mm, and temperature is raised to 230～270 ℃, and stirring velocity is 77r/m; The phosphoric acid that adds 0.064g adds the 0.135g tetrabutyl titanate and slowly vacuumizes, the stopped reaction when product of question response reaches the moment of torsion of setting, and behind the polymkeric substance that spues, pelletizing is subsequent use.

Embodiment 2:

Esterification: take by weighing the biogenetic derivation 1 of 558g, the DMT of 2-PDO and 748g puts in 4 mouthfuls of flasks of 2L, and adds the magnesium acetate of 0.28g, then temperature is raised to 160 ℃ rapidly; Treat the later intensification slowly of DMT dissolving, guarantee 1,2-PDO is not steamed, and outlet temperature is no more than 250 ℃; By the time stopped reaction when not having methyl alcohol to be steamed.

Polycondensation: polycondensation is with the polycondensation of embodiment 1.

Evaluation method:

Limiting viscosity (IV): adopt polyester national standard testing method: GB/T-14190-1993 tests.

Table: the limiting viscosity table of the polyester that makes

	Embodiment 1	Embodiment 2
			Limiting viscosity	0.65	0.76

Claims (3)

1. one kind is adopted 1, and the polyester of 2-Ucar 35 raw material is characterized in that: be by aromatic dicarboxylic acid or derivatives thereof and 1, and the macromolecule polyester that the 2-Ucar 35 obtains through reaction; Wherein 1, the 2-Ucar 35 is a biogenetic derivation 1, the 2-Ucar 35, and the carbon source is corn; Purity: 97%, pass through heat treated then, handle with the gac contact again; The biology 1 that processing obtains, the light transmission rate of 2-Ucar 35 when ultraviolet region 250nm is 65%, the light transmission rate during 300nm is 90%; The limiting viscosity of said polyester is 0.50-0.95.

2. employing 1 according to claim 1, the polyester of 2-Ucar 35 raw material is characterized in that: also contain carbon in the polyester and derive from the diprotic acid of petroleum and the copolymer composition of divalent alcohol.

3. according to the said employing 1 of claim 1, the polyester of 2-Ucar 35 raw material is characterized in that: said aromatic dicarboxylic acid or derivatives thereof is terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate.