Ester compounds, method of their production and the means for spooling the fiber

 

(57) Abstract:

Ester compounds of General formula I, where R is ethylene residue or alkyl substituted alkalinity residue with 2 to 4 carbon atoms in alkalinous chain, with stands, ethyl, propylene or isopropyl as alkyl substituent; "x" plus "y" is a number from 2 to 35 and not equal to zero; R1- - (CH2)z-; z = 0 or an integer from 1 to 12, or is phenylenebis or vanilinovy residue; m is an integer from 1 to 30. The compounds of formula I and their mixtures have both advantages easy biological assasinate with a slight swelling of polyurethane materials and suitable as a means for spooling the fiber, especially as texturebrush products and components texturebrush drugs. Complex oligoesters I get esterification diol of the formula II dicarboxylic acid of the formula III. 3 S. and 8 C.p. f-crystals, 5 PL. I

The invention relates to ester compounds, method of their production and their use as a means for spooling the fiber.

From US-A-4179544 and US-A 4227390 known polyoxyethyleneglycol that the heat treatment of the prepared synthetic fibers, as texturing, steam is required in relatively rare.

From EP-B-162530 known containing closed end groups of polyoxyethyleneglycol, which have good properties as a means for spooling the fiber and are also minor sedimentation on the fiber after heating processes.

However, all these compounds discover the disadvantage that they are only moderately biologically degradable, and consequently environmentally polluting waste water. Recently, requirements for biologically easily degradable means for spooling the fiber or textile auxiliary means are tightened. These requirements are intended to fall within the wastewater tektilnoy production means for spooling the fiber to neutralize the biological breakdown. The term "biodegradable" means that the means for spooling the fiber is split by biological, for example by containing in settling sludge settling install enzymes or bacteria. While it is desirable that the splitting was formed chemically simple compounds such as carbon dioxide, water, sulfate or phosphate. The definition of biological assasinate can be performed using various isnewbar/wave (OECD-302B-test).

In EP-A-538714 available ethoxylated diols as biologically easily degradable means for spooling the fiber. But these connections do not completely fill the gap. If the molecular weight exceeds 1200, they are not as readily biodegradable. On the other hand, described oksietilirovannye diols with molecular masses below 1200 problematic due to poor resistance to pressure, which is why they are not sufficiently protect the fiber under high mechanical stress during the texturing process. The consequence is damage in the manufacturing process and quality loss when texturing in the form of currents, broken fibers and capillaries. Another very common fault nizkozatratnyh diols and ethylenoxide/propylenoxide compounds is their tendency to cause swelling of polyurethane materials that are present in machines for textured in the form of knurling, drive belts or textured disks, which leads to premature wear of the units. Measure the compatibility of polyurethanes with textureloader drug in the special areas is the increase in weight (swelling) of the polyurethane materialSimritan 80 AU 991 item weight gain should be a maximum of 10%. Further, it should be noted that although with increasing molecular weight mentioned ethoxylated diols and ethylenoxide/propylenoxide compounds against the swelling recedes into the background, however, the biodegradation decreases.

Surprisingly it was found that the special ester compounds are good means for spooling the fiber and, in addition, easily biodegradable.

Ester compounds according to the invention are characterized by lower formula I.

< / BR>
where

R is ethylene residue, or once, or many times, mostly one - or twofold, alkylsilanes alkilinity residue with 2 to 4 carbon atoms in alkalinous chain and stands, ethyl, propylene or isopropyl as alkyl substituent, and preferred is methyl;

x + y = 2-35, and no x and y0;

R1-(CH2)z- where z is zero or an integer from 1 to 12, or phenylenebis or vanilinovy residue, and m = 1 to 30.

Preferably in the compounds of formula I

R - ethylene residue-CH2-CH2- , 1-methylethanol balance (isopropylene) residue or 2,2-dimethylpropylene balance, and Naib z=1-8, or phenylenebis or vinyl residue, and m=1-10.

Complex oligoesters of the formula I can be obtained by etherification diol following formula II

HO-(CH2CH2O)x-R-(OCH2CH2)y- OH,

where

R, x and y are specified for formula I, is,

dicarboxylic acid of the following formula III

HOOC-R1-COOH,

where

R1is indicated for the formula I is,

when a molar ratio of 1:0.25 to 1, mainly 1:0,45-1.

As diols or glycols are taken into account mainly those of the formula II, which have a molecular weight of 200-1500, where preferably 300-1000. Especially preferred are those in which R is isopropyl and which are those with isopropranolol as the source connection. Such glycols and obtaining them are described in EP 0166958 BI. Get them mainly so that the corresponding residue R in formula II picoline connection, for example ethylene glycol or isopropylalcohol, subjected to interact with by the same molar quantity of ethylene oxide, which corresponds to the sum of x plus y in formula II. In particular, as a rule, do this horizon vessel, then to create an inert atmosphere, washed with mostly nitrogen. Present under certain conditions, water is removed by applying vacuum. Then, when the temperature 110-170oC, preferably 120-160oC, dosed and is attached at a regulated pressure of a liquid or gaseous ethylene oxide. The completion of the accession of ethylene oxide install descending and remaining substantially constant pressure. To remove possibly present liquid parts of the obtained polyethylene glycol is maintained under vacuum within 0.3-1 hour at about 80-120oC. the Preferred alkaline catalysts are the hydroxide, carbonate or sodium methylate, and the corresponding potassium compounds. The amount of catalyst is usually 0.1 to 5 wt.%, preferably 0.3 to 3 wt.%, in calculating the number of entered pikolinos connection.

Used dicarboxylic acids may be aromatic or aliphatic in nature. Aliphatic dicarboxylic acids may be saturated or unsaturated. The aromatic dicarboxylic acid is mainly phthalic (benzene-ortho-dicarboxylic), terephthalic (benzene-para-dicarboxylic) and isophthalic (be with C1-C8-alkionovymi groups, such as malonic, succinic, glutaric, adipic, Emelyanova, cork, azelaic and sabotinova acid. Aliphatic unsaturated dicarboxylic acid is mainly fumaric or maleic acid. Of these dicarboxylic acids are preferred aliphatic saturated dicarboxylic acid, and maleic acid. Needless to say that instead of the dicarboxylic acids can be used and their derivatives such as corresponding anhydrides or halides, preferably anhydrides (anhydrides of dicarboxylic acids).

The esterification of diols of the formula II dicarboxylic acids or anhydrides of dicarboxylic acids of the formula III are primarily conducted without solvent, i.e. in the mass, and the cushion under a protective gas, and the reaction water Argonauts from the reaction mixture. The temperature of esterification are 170-230oC, preferably 180-210oC. the esterification Reaction is carried out mainly by acid or weak acid catalysis. Acid catalysis is carried out, for example, using p-toluenesulfonic acid, methanesulfonate or phosphonoacetic acid or mixtures thereof as a catalyst is strnewfile acid and NaOH in the ratio of I:I (in solid form or in the form of, for example, 1-50 wt.%-aqueous solution). A particularly preferred catalyst is a mixture of p-toluenesulfonic acid or methansulfonate and phosphonoacetic acid in a weight ratio of 1: 0.5, if phosphonoacetate acid is used as such (i.e. 100%), or in a weight ratio of I:I, if phosphonoacetate acid is used in the form of about 50 weight. % aqueous solution. This catalyst was prepared complex oligoesters the particular good quality regarding color and without sediment. The amount of catalyst can vary within wide limits. It is usually 0.03 to 0.5 wt.% based on the weight of diol and dicarboxylic acid or anhydride of dicarboxylic acids, preferably 0.05 to 0.2 wt.%.

The completion of the esterification reaction is determined by the acid number of the product of esterification, which should be less than 5, mostly less than 3 and especially preferably from 0.3 to 2.5. The product of esterification, which, after cooling to room temperature, subjected, if necessary, filtering, represents a target means for receiving fiber. The product typically has a viscosity of more than 500 mPas at 20oC, mainly 700-5000 and particularly preferably 900-3000 the lo hydroxyl groups), the saponification number and color index by iodometric scale. HE usually has a value of 10-160, preferably 70-115, the number of saponification 40-300, preferably 50-220, and the color index by iodometric scale < 0.1 to 20, mainly < 0.1 to 8 and particularly preferably < 0.1 to 1.

Ester products according to the invention can be used as such or in a mixture with other known means for spooling the fiber during manufacture and/or processing of fibers. Thus, a means for spooling the fiber consists of up to 100 wt.% ester compounds of the formula I or expressed otherwise, the tool according to the invention is characterized by the content or represents an ester compounds of formula I. as components of a mixture can be used known and common substances, such as polymers of ethylene oxide/propylene oxide, surfactants, ester oils from fatty alcohols and fatty acids, esters and salts of phosphoric acid, oxethylate lower alkanols or alkanediols, oxethylate fatty alcohols, oxethylate fatty amines and/or oxethylate fatty acids, which serve, for example, as agents of grease or knitting, emulsifiers, means the final finishing of value. %, preferably 30-60 weight. percent, the weight percentages calculated relative to the (finished) means for spooling the fiber. Thus, preferred according to the invention the mixture consists mainly of

(a) 30-60 wt.% ester product of formula I,

b) 5-20 wt.% saturated or unsaturated, linear or branched C8-C18-alcohol, ethoxylated 5-15 ethyleneoxide units, and

C) 20-50 weight. % diol of the above formula II, the weight percent calculated on (ready) mixture.

When spooling fibers using ester products according to the invention or their mixtures or mixtures of ester products according to the invention with other known means for spooling the fiber they are applied to the fiber usually in an amount of 0.1-1 wt.%, preferably in quantities of 0.3 to 0.5 weight. % percent calculated on the weight of (treated) fiber. The fiber material consists predominantly of polyesters, polyamides, polyacrylonitriles, polyolefins or copolymers. Application means according to the invention the material of the fibers is accomplished in such a way that the fiber is sprayed by means or which the fiber is conducted through the bath, which is a tool ky oligomeric product according to the invention has several advantages. He unexpectedly well biodegradable. This is all the more surprising that we are talking about structurally complex and relatively high-molecular compounds. Further, only few residues formed in the processes of heating and polyurethanes swell only very weakly. When used as a means for spooling the fiber described ester products are also required properties: they cause is also particularly desirable to protect the fiber elasticity. Thus, the ester products according to the invention and their mixtures have both advantages easy biological assasinate with a slight swelling of polyurethane materials, which is associated with little means to the residue and required to protect the fiber elasticity under pressure. They are therefore very well suited as a means for spooling the fiber, especially as texturebrush products and components texturebrush drugs. Complex oligoesters are usually water soluble, or dispersible in water.

Further examples of the invention are explained in more detail. Obtaining ester compounds according to the invention.

Example 1. In the reaction vessel with t is 1 mol) of the diol of formula II with R - isopropylene and x+y=12 (molecular weight 600), 50 g (0.5 mol) of succinic acid anhydride and 0.9 g (0.14 wt.% calculated on the total weight of diol and succinic anhydride) mixture of p-toluenesulfonic acid and phosphonoacetic acid in a weight ratio of 1:0.5 as catalyst. Downloaded the mixture under nitrogen atmosphere was heated to 200oC and at a temperature of 190-210oC kept under continuous vodootlivnye (approximately 6 hours), while the product of esterification is not acquired an acid number of approximately 0.7, and thus received after cooling, the oligomeric ester product according to the invention.

Examples 2-16. Other products according to the invention was obtained similar to example 1, the reaction conditions.

In table.3 summarizes examples 1-16, and the source connection, a diol and a dicarboxylic acid is used the molar ratio of diol to dicarboxylic acid and the following properties of the obtained ester oligomeric product: acid number (HT), the number of hydroxyl groups (CGG), saponification number (CHO), color index by iodometric scale (IRC) and viscosity (Elm) in mPas at 20oC. the Use of diols indicated in the table.3, for example, as "PEG GOOPR" (example 1) or PEG 300 PR" (example 3), which refers to polyethylene glycol (PEG) with molecular massac "PEG 300 ET (example 5) or PEG 600 ET" (example 6) diols are polyethylene glycol (PEG) with molecular weight, respectively, 300 or 600, moreover, the reference compound is ethylene (ET). For used diols are also still the sum of x plus y according to the formula II.

Test ester compounds according to the invention from the point of view of funds for the preparation of fiber.

From the obtained in examples 1-16 ester products tested - characterizing all other products of examples 1, 3 and 5 relative to the swelling of the polyurethane, evaporation and biological assasinate; ester product of example 1 was also tested regarding texturing.

- Swell tests polyurethane materialSimritan 80 AU 991 ( = registered trademark of Freudenberg): was determined by weight gain, which came after keeping the samples of the specified polyurethane for 7 days at 90oC in lonefire the product of examples 1, 3 and 5. Comparison test were used in example 1 diola. The results are shown in table. 3.

Test evaporation rate:

In the test for evaporation was kept, depending on the circumstances, 1 g of the ester product from examples 1, 3 and 5 at 220oC and determine the loss for 0.33 hours (20 minutes) and 24 hours, expressed in weight percent is the sky redeployment was determined using OECD test-30IE and test OECD-302B (definition of biological removal depending on time). In table. 4 shows the highest value of biological assasinate after 28 days for the ester products of examples 1, 3 and 5.

- The test of suitability as textureloader drug Test texturing was performed with three products according to the invention, namely with the ester product of example 1 (product I), with a mixture of 85 weight. % ester product of example 1 and 15 wt.% ethoxylated with 8 moles of ethylene oxide fatty alcohol (product 2) and with a mixture of 30 wt.% the ester product from example 5, 20 wt.% ethoxylated with 8 moles of ethylene oxide fatty alcohol and 50 wt.% used in example 1 atsetilirovanie diol (product 3), and for comparison were tested, in addition, normal polyoxyethyleneglycol and used in example 1 oksietilirovannye diol.

The tested products, depending on the circumstances, was applied during the spinning complex polyester fiber using a gear pump on the fiber. Below, in particular, lists the test conditions and data texturing:

- texturearray machine: Barmag FK 6/700

- titer spun fibers: a complex polyester POY (pre-oriented fibers) 260 genetics f 32 matt

- nanos: 0.35 wt.%

9

- D/Y (the speed at the circumference of the friction discs, divided by the feed rate of the fiber): 2,2

the temperature of both heating units: 205 and 180oC

- T1/T2the tension of the threads before Assembly and thread tension after Assembly): 62 CH 65 CH.

The tests were judged on how much total damage in the form of currents, broken threads and breaks capillaries manifested on 100 km of the obtained fiber. In table. 5 shows the number of injuries tested products.

As shown by the test results, ester products according to the invention have a surprising combination of properties from the point of view of preparation of fiber.

1. Ester compounds of General formula I

< / BR>
where R is the ethylene residue or once or twice alkyl substituted alkilinity residue with 2 to 4 carbon atoms in alkalinous chain and stands, ethyl, propylene or isopropyl as alkyl substituent;

x + y = 2 - 35, and x and y are 0;

R1is -(CH2)z- where z = 0 or 1 to 12, an integer, or is phenylenebis or vanilinovy balance;

m = 1 to 30, an integer.

2. Connection on p. 1 of General formula I, in which R is etileno chain and stands as alkyl substituent.

3. Connection on p. 1 of General formula I, in which R is ethylene residue, 1-methylethenyl the remainder, 1-methylpropanoyl the residue, 2-methylpropanoyl balance or 2,2-dimethylpropylene residue, x + y = 5 - 22, and x and y 0, R1is -(CH2)z- where z = 1 - 8, or phenylenebis or vanilinovy residue, and m = 1 to 10.

4. Connection PP.1 - 3 of the General formula I, where R is 1-methylethenyl balance.

5. The method of obtaining the ester compounds of General formula under item 1, characterized in that carry out the etherification diol of General formula II

HO-(CH2CH2O)x-R-(OCH2CH2)y-OH,

where R, x, y have the values given,

dicarboxylic acid of General formula III

HODC-R1-COOH,

where R1has the value

and the process is carried out at a molar ratio of diol and dicarboxylic acid 1 : 0.25 to 1 at 170 - 230oC, the etherification is carried out to obtain a product of esterification with an acid number less than 5.

6. The method according to p. 5, characterized in that the diol and dicarboxylic acid is injected at a molar ratio of 1 : 0,45 - 1.

7. The method according to p. 5 and/or 6, characterized in that the esterification is carried out at 180 - 210oC and K is ASEE ester compound, characterized in that it as ester compounds contains at least one compound of formula I under item 1.

9. Means under item 8, characterized in that it contains 5 to 95% by weight means, at least one ester compound under item 1.

10. Means under item 8, characterized in that it comprises 30 to 60% by weight means, at least one ester compound under item 1.

11. Means under item 8, characterized in that it comprises in the main a) 30 to 60 wt.% at least one of the ester compounds on p. 1; b) 5 to 20 wt.% the ethoxylate with 5 - 15 ethylenoxide links of C8- C18- alcohol and b) 20 to 50 wt.% diol of the formula II under item 5.

 

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