DE1793666C3 - Polyisocyanates and processes for their preparation - Google Patents

Description

",. _(n ", _Nrn1 phosgene into the corresponding acid chlorides and

IR-J-L- (CW ₄ ) JfINi-UJx. ~ $ mh _{the aBSC} closing reaction of the thus obtained

m ^ t , „,„ ο make acid chlorides with a metal azide. the

in the y is O or J χ ejnen value of 2 gu "CWA" a ^ ymeren fatty acids are easily

up to about 4 and R den. «^ j ^ J« ^ ¹ Jf. _1O £ S £ * £ 2l the corresponding polyisocyanate

polymeric fatty acid representing, ^since f ^{'r h} * J ^ * _Dje reactions may in the case of

Jcennz ^ ehne ^ You can either use Ajjfc ™ J «^ _{dimeric fatty} acid as the starting

from pol »fatty acids · ™ ^ 2Α ££ IuSf Srcb repeat the following equations-

amines of polymeric fatty acids with phosgene. maicu <u "" "-

2. The general idealized polyisocyanates are given.

Formula ¹⁵

₊ 2PQ ₃ _ »3 R (COCl) ₄ + 2H ₃ PO ₃
in which y is ZaWO or 1, χ a value of 2 R (COCl) ₂ + 2NaN ₃ -> R (CON ₃ ) ₂ + 2NaCl

up to about 4 and R is the hydrocarbon radical of R (CON ₃ ) - * ■ R (NCO) ₂ + 2N ₂

represent polymeric fatty acid. ^ao

In this way, such poly-

The invention relates to easy production of polyisocyanates and verisocyanates in which y is equal to 0. drive to their ^ position. The polyisocyanates are "5 The polyamines polymeric ^^ '^' Wh intermediates for preparing polymeric as Ausgangsmatenal for £ e erfindungsg ^e ™ ^a ^ ^Re ^ - compounds with very good properties. The subject of the invention is a process for the production of mere fatty acids via the nitriles and their subsequent hydrogenation. The implementation to the idealized formula 3 ° Polynitrile is in the 2nd chapter of the book »Fatty

.dealized formula ^ ^ ^^ _Derivativesi of AW R a 1 st ο n,

mjr (cn \ > 3CO1 John W i 1 ey and Sons, Inc., New York (1948), be

[RII- (LH ₂ ) VNLUj ₁ , wrote. The hydrogenation of the polynitriles works well

in which y is the number O or 1, χ has a value from 2 to in the presence of ammonia and of a Katoly-

about 4 and R is the hydrocarbon radical of a polymer such as Raney nickel. If a dicocyanate is produced

represent meren fatty acid, characterized, to be made, can be a relatively pure dimensioned

that either azides of polymeric fatty acids are used as starting materials.

heated or polyamines of polymeric fatty acids with Next can be the corresponding dimeric Nitnl or

Phosgene converts dimeric amine to be distilled, with a dimeric

The invention also relates to polyiso 4 <> Amine is produced as a high-purity starting material.

cyanate's general idealized formula The polyamines are then mixed with phosgene

implemented, whereby the inventive poly

R - [(CH) _v NC0] i isocyanates are formed. This procedure can be used for

the case of using dimeric fatty acid than

in which y the number O or 1, χ a value from 2 to 45 starting material represented by the following equations about 4 and R the hydrocarbon radical of a poly-:

R (COOH) ₂ + 2NH ₃ -> R (CN) ₈ + 4H ₂ O

^ R (CH ₁ NHA

R (CH ₂ NH ₂ ), + COCl ₂ - _A > R (CH ₂ NCO) ₂ + 2HCl

This process can be used to produce polyisobond and triple-bond unsaturated acids Easily produce cyanates in which ν is 1. one. The term "polymeric fatty acid residue" relates to

The polymeric fatty acids, which are divalent, trivalent and polyvalent carbon ends as starting compounds for producing the polyhydrogen radicals according to the invention, dimerized fatty acid, trimerized Isocyanates are useful, are replaced by polymeric fatty acids and higher polymeric fatty acids. This made of a fatty acid. The residues which are divalent and trivalent here are referred to here as The term "fatty acid" used refers to "dimeric fatty acid residue" and "trimeric fatty acid residue" referred to naturally occurring and synthetic, mono- 65.

basic, aliphatic acids with carbon chains The saturated, with double bond and triple

from 8 to 24 carbon atoms. The term unsaturated fatty acid bond will be general "Fatty acid" thus includes saturated, poly-

3 4

merized, but based on 4 functional similarities - distillation and solvent extraction carried out

lceit the polymerization products will be the same. The use of relatively pure dimerized fat

generally referred to as "polymeric fatty acids". acids as a starting product is advantageous where the

Saturated fatty acids are difficult to use in poly-diisocyanate for making a monomer

merize, but the polymerization can result in the recovery of linear, high molecular weight polymers

elevated temperatures with a peroxide, such as di-tert.- should be applied relatively trimerized

Butyl peroxide can be achieved. Because of the low fatty acids can be applied where one

Yields of polymeric products show the same high purity diisocyanate is desired. It

no industrial importance. Mixtures of the polymeric

Saturated fatty acids include branched and χα based fatty acids for making mixtures of the

Straight-chain acids such as caprylic acid, pelargonic acid, polyisocyanates can be used. Each of the described

Capric acid, lauric acid, myristic acid, palmitic acid, unsaturated polymeric fatty acids can occur

Acid, isopalmitic acid, stearic acid, arachidic acid, the use of these in obtaining the poly

Behenic acid and lignoceric acid. isocyanates are hydrogenated.

Acids unsaturated with double bonds can be polymerized. The polyisocyanates according to the invention can be polymerized much more easily. It can handle kataiy- with unexpected ease. So table or non-catalytic polymerization processes are the same characterized by very low toxicity to be applied. The non-catalytic polymer and have a long life due to their slowing generally require a higher temperature. samer implementation with moisture. Suitable agents for the polymerization are acidic 20, in particular for the production of polymers, aus- or alkaline clays, di-tert-butyl peroxide, boron traversing polyfunctional organic compound fluoride and other Lewis acids, anthraquinone, fertilize the active hydrogen atoms Consider ent-sulfur dioxide and the like to be suitable monomers. It has been found that the branched-chain and straight-chain polyisocyanates according to the invention and unaccepted condensation polymers containing several or one double bond, such as 3-octenonic acid, 11-dodecenone, can be prepared without difficulty. The reactions of other acids, linderic acid, lauroleic acid, myristolein isocyanates, such as aromatic diisocyanates and amines, acid, tusuzic acid, palmitoleic acid, and petroselinic acid are extremely difficult to control. In addition, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, the polymers produced in this way have good cetoleic acid, nervonic acid, linoleic acid, linoleic acid, flexibility and are easy to shape. Polyacid, timnodonic acid, eicosatetraenonic acid, nisi ureas and polyurethanes made from acid, eleostearic acid, hiragonic acid, moroctinic polyisocyanates according to the invention are tough and absorb ninic acid, scoliodonic acid and chaulmoogric acid. only extremely small amounts of water.
When the fatty acids polymerize, they react. 11
according to a mechanism similar to that of Diels-Alder 35 Example 1
The reaction is very similar to one another, with poly-In a 1-liter round bottom flask with reflux condenser, mers are formed which contain one ring or more rings of the containing a calcium chloride drying tube, see US Pat. No. 3,475,406 and which protects will be 200 g of purified dimerized literature cited therein. Fatty acid dissolved in 200 ml Skellysolve B and 65 g

Triple bond unsaturated fatty 4 ° phosphorus trichloride introduced. The dimerized fatty acids, like isanic acids and isonolinic acids, acid is obtained from the acid mixture in tall oil also polymerized with recovery of polymeric acids and consists mainly of dimerized ninolized that can be used. Triple and oleic acids. It has the following self-tie containing unsaturated acids only occur: 99% by weight of dimerized fatty acid, seldom found in nature and can be found costly 45 0.5 wt.% monomer, neutralization equivalent 286 synthesize. For this reason the same to and saponification equivalents are 280. The conversion time not accessible to any industrial significance. mixture is refluxed for 2 hours

Although any of the above-described sows are kept and then left over saturated, double and triple bond unsaturated night stand. The clear solution of the dimerized fatty acids Acid chloride is used to produce the polymeric fatty acid 50 from the heavy phosphoric acid can be applied, there is general poured off. The solvent and the excess Practice in making mixtures of the acids (or the simple phosphorus trichloride) under reduced pressure aliphatic alcohol ester, d. H. the methyl ester, too deducted.

polymerize as obtained from the naturally occurring In a 1 liter flask with cooling coils, stirrer drying and semi-drying oils 55 and thermocouple will be a solution of 30.4 g. Suitable drying or semi-drying sodium azide in 125 ml of water which has been ^{oiled to 10 0} C include soybean, linseed, tall, tung, and other cools, introduced. A solution of 100 g of dimerized flower and dehydrated castor oil and the like is added to this rapidly stirred perilla and oiticia cottonseed, corn, sun solution. The fatty acid chlorides dissolved in 150 ml of acetone, the most easily accessible acids are oleic acid and 60 The reaction temperature is kept during the addition of linoleic acid, so that the same as the starting materials set and 1 hour after the addition at 10 to 15 ° C for the preparation of the polymeric fatty acids, and then 200 ml are kept. It is preferred to add heptane as starting materials. The heptane layer is separated, the relatively pure dimerized polyisocyanates are prepared, washed with 2 parts of cold water and then fatty acids are used. Such acids can be dried from 65 over magnesium sulfate. To 200 ml of heptane, mixtures are obtained that contain the monomers that are ^{kept at 65-7O 0} C, the indicated merized fatty acids, trimerized fatty acids and dried heptane solution and the dimerized fatty higher polymer by adding a high vacuum acylazide. The solution is at 1 hour

65-70 ° C and then the heptane is derived from fatty acid. The diisocyanate is a light

deducted under reduced pressure. This gives 70 g of a brown oily liquid.

liquid diisocyanate of the following formula Example 5

OCN D NCO, 5 The procedure according to Example D with

the exception that repeats the dimeric amine before

in which D is the dimeric fatty acid residue that is hydrogenated from the reaction. 179 g are obtained

Starting product used dimer fatty acids acidic diisocyanate, which is practically the same

hard. Properties like the diisocyanate of Example 4

_B. . .- ίο, but has a lighter color.

ueispiei ί ρ. _He fi _{n (} proper connections can

The procedure is as indicated in Example 1, with easy-to-use polyureas and polyurethanes, with the exception that 94 g of dimerized fatty acids are used, as shown below:
chloride in 140 ml of heptane instead of acetone - A solution of 4.41 g (0.01 equivalent) of tetra can be dissolved. 63 g of diisocyanate are obtained. 15 methylenediamine in 400 ml of methylene chloride was at

Room temperature in a Waring Blendor vigorously

Example 3 stirred. 29.80g (= 0.10 equivalent) of the

The procedure described in Example 1, with the game 5 obtained diisocyanate were in 80 ml

Except that 213 g of dimerized fatty acid chloride dissolved methylene chloride and quickly became that intense

be dissolved in 300 ml of acetone. 177 g of stirred diamine solution are obtained. The polymer

Diisocyanate. precipitated practically immediately after mixing. the

In the case of the polymer slurry obtained, the mixture was stirred for 10 minutes.

^P 200 ml of n-heptane were then added and the

140 g (2.42 mol) of phosgene in 700 ml of mixture were stirred for a further 10 minutes.

dry toluene and cooling in an ice bath at 25. The polymer was filtered off and im

Keeping the solution temperature below 5 ° C dissolved. The vacuum dried. It is loaded with polymer A

Phosgene solution is drawn into a 2 liter three neck flask.

introduced, the one with dry ice condenser, stirrer and For comparison, was like in a second experiment

Dropping funnel is equipped. A solution of the above is used, but was used as a diisocyanate

164.4 g (0.6 equivalents) double-distilled di- 30 octadecamethylene diisocyanate, OCN - (CHg) ₁₈ - NCO,

merem amine in 200 ml of toluene in the dropping funnel (16.83 g - 0.10 equivalent) used. Here is

introduced. The diamine is obtained by filtering a polymer B.

dimeric nitrile in the presence of ammonia and The polymer A prepared according to the invention is

Raney nickel catalyst moistened with methanol has a melting point of 180-183 C, while

manufactured. The dimeric nitrile becomes from a dimeric polymer B has a melting point of 238-240 ° C

ized fatty acid produced, which has from an acid. However, the polymer A remains in a molten state.

mixture is obtained in tall oil, the acid being zenem state liquid and faintly colored, and a

mainly from dimerized linoleic and oleic acids decomposition is down to a temperature of about

consists. The dimeric amine has the following inherent 250.degree. C. not recognizable. In contrast, this shows

transactions on: 0.5 ° _o wt% monomer, 98.5 weight polymers B 40 at about 250 ⁰ C a considerable decomposition..

Dimer, 1.0% trimer and neutralization equation, which can be seen from the fact that it is initially viscous

valentine 271st and then becomes rubber-like. According to the invention

Utilizing a heating jacket of the polymer A produced is therefore total warms a considerably flask until a strong back flow of the larger scope (180-250 ⁰ C), is observed in the phosgene (40-50 ⁰ C). The dimeric 45 it is processed and, if desired, reprocessed amine solution is then slowly within a can without decomposition occurring. The PolyStunde added. After the addition to the termination mere B has only had a very limited application, the conversion mixture will range from 238-250 ° C.

refluxed for a further 2 hours. The dry-In addition, the polymers have the following own ice cooler is replaced by a water cooler and 50 shafts (ASTM-D-1708; the test specimens were used at the temperature of the solution is slowly increased to a pressure of about 850 kg / cm ² and at Tempeiadas Toluene begins to flow back in. Further doors of 180-183 C [polymer A] and 238-240 C are refluxed for 6 hours, and then [polymer B] is pressed):

Heating canceled. One leaves the solution on

Cool down to room temperature. Then the toluene 55 becomes polymer A polymer B

peeled off under reduced pressure. You get

81.4 g of isocyanate of the formula tensile strength, kg / cm ²

Yield stress, kg / cm ²

OCN - CH ₂ - D - CH ₂ - NCO, elongation (%)

60

in which D is the dimeric fatty acid residue resulting from the These data show that polymer B is stronger, but

used as the starting compound dimerized is considerably less flexible than the polymer Λ.

336 545 331 523 330 195

Claims (1)

meren fatty acid idarstellen, as well as the use of these Pojyisoeyanate for the production of polymers. · 'Η ι · «« «Use Dae as starting material for the synthesis 1. Process for the preparation of _{Polyisocyana- j} _we ^, £ ^w ^; ^ _{ftIvm (} , ", _{n Fi} , _n5älirf . _N , -,""" _ci "" W ^ «V ^ fatty acids can be ^ l Fä i g ^^ fatty acids can be ten of the aügeroeinen idealized formula __ ^^ _{Implementation} of polymeric fatty acids with z. B.