PL102928B1 - METHOD OF MAKING TRANSPARENT GLAZED POLYAMIDE - Google Patents

Description

The invention relates to a manufacturing process the glass of a transparent (translucent) glass liamide.

Polyamides or copolyamides have been known for a long time when amines of the "dicycan" type [di- / 4- -aminocyclohexyl) -alkane compounds] as well 4,4'-diaminobicyclohexyl. However, everything The copolyamides obtained so far show disadvantageous features or their abilities processing, or about their mechanical properties in other words, with regard to the transparency stability in boiling water or organic liquids or solutions, or the price of frightening raw materials.

In general, liquid isomer mixtures are used these amines. The class of amines of the "dicycan" type remained already described in the Big Block Patent Specification cheap No. 619,707. Although copolyamides were obtained some of the diamines mentioned in this patent They already have good properties, however, it is half it is required to further improve their capacity to do so processing and other properties such as durability, transparency relative to boiling water as well resistance to the action of solutions and solvents tics and hydrolytic reconstruction. It represents purpose of this invention. There is also an interest not recipes that allow application cheaper raw materials.

The above and other known methods of preparation transparent copolyamides with diamines of the "dicycan" type (Swiss patent 449,257, U.S. Patents US America no. 2 494 563, 3 842 045, 3 840 501, Japanese declaration 7,211,502) use diamines of the head in addition to "dicycano" not long-chained relatively expensive diacids carboxylic acids such as azelaic acid, sebacic acid, dodecanedicarboxylic acid to arrive at the product of materials showing tolerable machinability, not too high melt viscosity, e.g. less than 10,000-20,000 poise at 300 ° C.

If only the acid component is used the relatively cheap adipic acid was obtained they eat often colored end products which glass transition temperature and melt viscosity This is so high at the temperature conventionally used processing temperature in order to reduce this temperature peratura it is necessary to add a special composition of the so-called AH salt (adipine acid salt) new and hexamethylenediamine) or caprolac- tamu. Correspondingly produced polyamides have low resistance to hot water and dissolving couplers and show relatively high ability water absorption with the injection method are related to occurring during conditioning changes the volume of the shape.

Description of St. US No. 2 696 482 describes transparent polyamide made of "dicycan" and iso- phthalic acid, having good resistance to hot water de.

For the favorable course of the condensation reaction 102928102928 however, it is necessary to start from the diphenyl acid ester isophthalic or add polyclonal to the mixture phenol densation as solvent either softener. Due to the high temperature softening and high viscosity in the molten state obtained polyamide alloys, it is necessary processing temperature approx. 330 ° C. Maximum The water absorption of this product is 7.75%.

Also listed in U.S. Patent No.

US No. 3,847,877 copolyamides with copper mixtures of isophthalic and terephthalic acid, incl moreover with nylon 6 as an ingredient special, show a similarly great ability to ab- water sorption and, after treatment, boiling little water I tend to grow dark after a few days.

Mentioned in U.S. Patent No. US

No. 3,597,400, transparent polyamides, fin formed from a mixture of isophthalic acid and tere phthalic acid and a mixture of "dicycan" and diamino of phiohexane with a high proportion of diaminohexane as a diamine component, they show too much for its ability to absorb water. When stored When such polyamides are present in water, the temperature is soft the temperature is lowered to 50-60 ° C.

It has now surprisingly been found that it is possible to make transparent like glass (translucent polyamides with good mechanical properties and excellent transparency resistance to boiling water if a mixture consisting of a) diamine with the formula given in the drawing where Rx and R2 independently of each other mean each of them atoms hydrogen or methyl radical a n = 0-6 and atoms hydrogen of both cyclohexane rings partially or they can be completely replaced by metal radicals rear and with b) more or less stoichiometric Quantities (for diamine according to a) % isophthalic acid that can be replaced by w 0-50% (mole or weight) terephthalic acid % and with up to 15 mole% (vs. to the total amount of said acid or of said mixture of acids) can be replaced with other polyamide-forming dicarboic acids xyl compounds and with c) 30-40 weight percent, with respect to the sum of a), b) and c) of further poly- a quaternary ingredient which may be cyco-ami- the acid or its lactam of more than 9 atoms carbon or salt or a stoichiometric mixture for 1: 1 aliphatic dicarboxylic acid, in particular, α, ω-polymethylene dicarboxylic acid and aliphatic diamine, especially a, co-poly methylenediamines, undergoes polycondensation it is necessary that the average number methylene groups, referred to each group amide or to each pair of amide-forming groups, was at least 9 and whereby the least higher number of methylene groups between groups amide-generating compounds was at least 6 and in when part of the isophthalic acid is replaced total aliphatic dicarboxylic acid the proportions by weight of this aliphatic acid of dicarboxylic acid (DCS) and additive c) is in Appendix in the range of 30-40% by weight (based on the sum of a), b) and c)).

There is a deer, it is understood that in 40 50 55 60 this definition can also be used everywhere mixtures of such additional ingredients. If according to ci and c2 several compounds or pairs are used salt is then a condition for the average number of groups pertaining to each group of amide to each pair of amide-forming groups of should be at least 9, this applies to the total all used add-ons.

As diamines of the "dicycan" type according to a) table mainly bis- (4-amino-3-methyl- cyclohexyl) -methane and 2,2-bis- (4-aminocyclohek-) sylo / -propane. But you can do valuable products that can be produced with 4,4'-diamino-bicyclo- hexylmethane and 1,2-bis- (4-aminodicyclohexyl) - -ethane. In practice, the usual ones are used, e.g. but at a temperature of 25 ° C the mixture of isomers of this a kind of diamino compound.

The acid components according to b) apply preferably isophthalic acid alone or v trading a mixture of isophthalic acid and terephthalic wego. If up to 15 mole% of isophthalic acid or mixtures of isophthalic acid and terre phthalic acid is replaced by other diacids the boxyls forming the polyamide then as such acids are used, such as acids containing preferably more than 6 C atoms, Newly cork, azelaic and sebacic acid, dodecanedicarboxylic acid and their base homologues wrapped in a side chain. Preferably not use any other polyamide-forming acid dicarboxylic owls.

As a third component forming polyamide according to c) in particular the following applies: for Ci: aminolauric acid- new or preferably its lactam or amino acid undecane, for c2: salts of the following diamines and dicarboxylic acids, viz - diaminoalkanes and α, ω-alkane dicarbohydrate acids xyls and their homologues substituted in side chain. Diamines: 1,6-diaminohek- san, 1,8-diaminooctane, 1,9-diaminononane, 1,10- -diaminodecane, 1,12-diaminododecane, trimium- Tyl6-methylenediamine. Dicarbo- xylic acid: azelaic acid, sebacic acid or dode canodicarboxylic acid.

The mentioned diamines and dicarboxylic acids we can be freely combined to make salt.

An example is the 1,12-diaminododecane salt and the acid su dodecane dicarboxylic acid and acid salts azelaic or sebacic with diaminohexa- nem, diaminooctane, diaminododecane or diaminononane. Under the term "amide groups" creative "is therefore the vapor - NH2 and COOH.

A reactive derivative of the group would also be possible —COOH, such as an ester or a halide group that is, the acids mentioned could be used dicarboxylic e.g. as chlorides or esters methyl or ethyl. Basically the same can It would also be possible for the acid component of the wine debt b).

In practice, however, preferably free is used Swucarboxylic acid. It is apparent that for cx compounds the equivalent weight is identical tic with molecular weight. For salt or ste- chiometric mixtures of diamine and acid of the dicarboxylic type c2 (it is half9) pre-condensation and the main amount of reaction water cji distils itself. It also increases something once more the viscosity of the molten substance. Because the temperature is now rising steadily with the after a period of about 1 hour, the value is reached 280-300 ° C. Each rehearsal ends in general with a condensation time of 3.5-6 hours.

The stirrer is removed from the molten substance, and I am it knocks out of the glass tube itself after it solidifies. By the analytical data of the marking at the end of the table on completely transparent materials.

Examples IX-XII. In the examples IX-XII the amine was again 4,4'-dimethyldi cyclohexylmethane and as an additive amino acid lauric. The molar ratio of diamine to acid dicarboxylic acid and additionally it was all cases 1: 1: 1.1. In the example IX was used as the dicarboxylic acid JPS-85 [isophthalic acid containing 15% acid terephthalic acid (Amoca)]. In the examples X, XI and XII part of the JPS-95 component was replaced with an aliphatic one dicarboxylic acid. £ array visible is that the amine ratio is constant in each case: : acid: amino acid by partial replacement of the aromatic acid component will deteriorate and the glass transition temperature loses also stability of transparency in boiling water.

Here too you receive in all cases transparent polyamides suitable e.g. for injection.

The performance of the tests corresponds to the description of tests 1-8.

Examples XIII-XV. In Examples XIII, XIV and XV molar ratio amine: acid: amino the acid is again 1: 1: 1.1. The acid used was JPS-95 was reintroduced as an additional component aminolauric acid. As an amine component, mixtures of different amines were partially used according to the invention, therefore, in Test 13, mixes nine 1: 1 (minor parts) 4,4'-diamino-3,3'-two- methyldicyclohexylmethane and 4,4'-diamino- dicyclohexylmethane and a mixture in Run 14 (1: 1) 4,4'-diamino-3,3'-dimethylbicyclohek- methylmethane and 2,2-bis- (4-aminocyclohexyl) -propa nu. In Test 15, the amine component was used there is 4,4'-diamino-dicyclohexylmethane.

In all three cases you get beautiful transparent products that work well for use e.g. for injection. Performing the trials corresponds to tests 1-8.

Examples XVI - XVII. Molar ratio amines for JPS-95 were selected in all cases as 1: 1. Of the class of amines as defined by the excerpt taken 4,4'-diamino-3,3'-dimethylcyclohexyl- methane for examples XVI, XVII, XXI and XXII and 2,2-bis (4-aminocyclohexyl) propane for example Clades of the eighteenth and nineteenth centuries, and in the case of sample 20, taken 4,4'-diamino dicyclohexylmethane. As additive component according to c) being applied beyond the definition of compounds such as caprolactam or AH salt in an amount of about 25-36% by weight. 2928 If the share by weight of the allowance beyond the de¬ the fineness was 34-36% by weight of the extract no products that have become opaque boiling water after a few hours. If attending molar of these additives as in the case a particularly preferred laurinolactam is 1.2 up to 1.0 mole of additive per mole of acid according to b) (corresponding to the weight fraction of the additive only not about 25%) then you get the products with markedly worse mechanical properties all. The performance of the tests corresponds to the description of the tests 1-8.

Example XXIII. In an autoclave for polikon- densation, 11.50 kg of the liquid mixture are mixed 4,4'-diamino-3,3'-dimethylbicyclo- isomers hexylmethane and 10.50 kg of laurinolactam with 3 kg water by slowly heating to 180 ° C.

Then, stirring-poured into the melt continuously one quarter of an hour 8.0 kg isophthalic acid ty- pu JPS-95 (Amoco, USA) so as to create one A birth suspension to which 29 g more is added benzoic acid as well as 3 g of the detergent ciwfoam based on silicones. The autoclave starts is now flushing gas-tight so that the melted sub- the bed is under a pillow of steam.

The molten material is then heated with stirring up to 280 ° C. It also produces itself pressure of 20 atm which remains for a while days. The pressure then slowly drops to atmospheric pressure and molten substances condenses within 2 hours at temperature 280 ° C under a nitrogen stream. Temperature at last The alloy is raised to about 300 ° C and stirred for a long time pour in about 4 hours until it is found no longer any increase in melt viscosity. Then the product is removed from the autoclave and granulated. He is it has a relative viscosity of 1.5 / 2 and a viscosity bones in the molten state 10,500 poise at a temperature at 280 ° C under a load of 12.5 kg. Tenipera- The 40th glass transition is 151 ° C.

On an injection molding machine with a cylinder temperature of 280 ° C ASTM stretched samples and male be- cure and on them mechanical properties are marked ne. Flowability and strength to The stretching according to DIN 53455 was sequentially 950 and 650 kg / cm2. Ultimate bending stress according to DIN 53452 it was 1200 kg / cm2. At impact testing according to DIN 53453 is not excluded crack in the material melted. Notched impact strength According to DIN 53453, the amount of material was 2 cm kg / cm2.

The material had a ball hardness according to VDE0302 1100 kg / cm2 after 60 seconds. ; Commercially available transparent polyamines in the mentioned conditions, they showed approx 55 twice as much moisture absorption. As a result comparatively very little moisture absorption also in water the mechanical properties of the material rialu change very little. In addition, he became number of dimensions of polyethylene injection moldings The midium of the invention is very good. 102928 14 cont N i — i CC fi \ < and ^ ^ JL a cd1 n S £ n 9 - ¦s 3 «g ^ Q «n M 10 1 ^ o ~ g horse- tions '^ cd S fi s 0 $ -i TD £ Xl > M. 'S • N WHAT about S. * * 0 What fi < Mi 5§ >> fl ^ a w a> w W) O S O O g cd r « in cd about hJ ¦§ < 73 WHAT PL, * p -O> » at 5 'cd S in cont rVI >> cd> fi- 2 S. 'cd N 73 ABOUT cont PL, cont at Xl ABOUT 73 ABOUT about about about l-H 1–1 CS | CS] CD l — i about 00 CSJ 10 WHAT 1–1 1–1 1–1 l-H O LO LO fi cont o cont fi o Q Q What 1–1 cont .ABOUT ABOUT 73 ABOUT about about ^ CS] LO l— ( c- C- CD loam ABOUT about What LO 1— ( 1–1 rH O LO LO r! fi "vol a & Q Q i-H ABOUT cd ^ "3 fi 1 S £ ° <=> L> - What loam WHAT What What 1–1 ° 00 csi What What" ^ 1–1 l-l <=> about fi cont 0 <-> Q LO i-H P * W N O G & o 'a? £ JS "o >> ojO r. and*" S-S a n cn n H o Background about ^ cd c fi 73 ABOUT • ^ o M cd fi cont fi about cd cu CU cd o 73 ABOUT 73 Ul Pl, ABOUT 73 ABOUT cont .Q -about at Mon in O ™ N N 73 N o o o o o o o o o o o o o o O LO O O O O O CD CO O i-H I> i-H CD CO t-H rH CS] rH L> - CO About LO ^ ^ CD CN LO LO ABOUT LO r- about LO ABOUT CXI LO csi LO CD o o o o o o o what what CM CSI LO LO O ^ LO LO O O ^ LO "LO ~ LO *" LO * "CD" LO ~ C- t- CSI rH CSI CO (M CO CD O CD ^ ^ CS | ^ ^ CSJ CO CO CSJ CO -oidjE ^ HV I9S cont about cont about about AXIS and Q Q102928

Claims (5)

Patent claims 16 A method of producing a vitreous transparent polyamide, characterized in that a mixture consisting of a diamine of the general formula given in Figure 1 in which R x and Rg independently of each other denote each of them hydrogen or the methyl radical an - 0 - 6 and the hydrogen atoms of both cyclohexane rings can be partially or completely replaced by methyl radicals and b) a more or less stoichiometric amount [with respect to diamine according to a)] of isophthalic acid, which can be replaced with 0 - 50% (mole or weight) acid Terephthalic acid and up to 15 mole percent (based on the total amount of said acid or said mixture of acids) may be replaced by other polyamide-forming dicarboxylic acids and with c) 30-40 weight percent, based on the sum of a ), b) and c), a further polyamide-forming component, which may be cx) ω - an amino acid or its lactam of more than 9 carbon atoms or c2) salt or a stoichiometric mixture of 1: 1 aliphatic dicarboxylic acid, in particular α, ω-polymethylene dicarboxylic acid 10 15 20 25, and an aliphatic diamine, in particular α, ω-polymethylenediamine, is polycondensed, the average number of methylene groups relating to each amide group or to each the pair of amide-forming groups is at least 9 and the smallest amount of methylene groups between the amide-forming groups is at least 6, and in the case of replacing a part of the isophthalic acid with an aliphatic dicarboxylic acid, the sum of the weight fractions of this aliphatic dicarboxylic acid ( DCS) and an additive in the range of 30-40% by weight [based on the sum of a), b and b)]. 2. The method according to claim A process as claimed in claim 1, characterized in that bis- (4-amino-3-methylcyclohexyl) methane is used as the diamine of type a). 3. The method according to p. The process of claim 1, characterized in that the bis- (4-amino-3-methylcyclohexyl) -methane isomer mixture is used in liquid form. 4. The method according to p. A process as claimed in claim 1, characterized in that isophthalic acid is used as the acid component according to b). 5. The method according to p. A process as claimed in claim 1, characterized in that the third polyamide-forming component according to c) is an aminolauric acid or a lactam thereof. , h2n- (h} tc4 {h) -nh Wsór -i W.Z.Graf. Main - 2388/80 - 95 Price PLN 45