DE1645498A1 - Process for the production of polyamides - Google Patents

Description

FATENTANWirlT '·

DR. E. WIEGAND [MPL-ING. W. NIEMANN 16 4 5 49α

DR, M. KÖHLER DIPL-ING. C. GERNHARDT

MONKS HAMBUR-G

TELEPHONE, 555 474 8000 Mö N CH IN 15, 12. Mfti 1970

TELEO COMB: KAHPAYENT ■ NUSSBAUMSTRASSE 10

W. 12 763/66 15 / Ko / Loe P 16 45 498.1-44

Limitod
Osaka (Japan)

Process for the division of polyamides

The invention "relates to a novel ancestor for the anionic polymerization of anhydrous lacta-

> I.

men and in particular to a process for anionic polymerization of "lactams using a phosphinimine, which is explained in more detail below. -

The polymerization of ι ** - lactams by an alkaline polymerization catalyst is known; It is also known that you can accelerate this alkaline Polymeres ation of ω- lactams, through the use of a mixed or Co-Xatalysatoi3. As cocatalysts for this purpose, N-acyl lactams, carboxylic acid halides, carboxylic acid esters, acid anhydrides, nitrous acid esters, isocyanates, halogenated phosphorus compounds and the like have previously been proposed. .- .009844 / 1678

an (Art. 7, Paragraph 1, Paragraph 2, Wr. 1 sentence ad «sÄndefungsg ^ 3, v. 4-D. 19Ö7),.,.,

BATH ORIGINAL

However, on an industrial scale, the anionic polymerization of lactams in the presence of such a Koodor mixed catalysts hardly described as satisfactory v / earth. .

For example, the anionic polymerization process is used in Giäii- or Pressfofmvoro ^ GdQ an ^ awendoti and ia. industrial scale for the production of solid polyamide fibers directly from its monomer, <£ -caprolactam, executed. This process, known as uromer gionon, is a process in which a mixture of the AP lactam, a catalyst and a co-catalyst is poured in the molten state into a mold in which the polymerization is carried out under atmospheric pressure to effect direct shaping. However, if it is desired to produce a particularly large molded article. various difficulties arise. Thus, in the polymerization of this type, the reaction rate is so great that it is difficult to convert a uniformly mixed solution of the lactam, a catalyst and an ic catalyst into a predetermined form during the casting, and the polymerization with such a rapid generation of Polymerization change is achieved that the control of the polymerization to appropriate conditions is difficult and accordingly uniform polymerization is hardly expected. In addition, due to the volume -.

009844/1678 ^:

BADOfIlGlNAL

decrease or decrease the tendency to the occurrence of voids and other defects and furthermore these phenomena particularly tend to occur in the vicinity of the center of a product and in parts where the thickness changes · Due With these phenomena it is generally difficult to obtain a homogeneous product; rather, products are preserved which not only have defects in physical properties but also in appearance and shows error.

The object of the invention is therefore to create a novel process for the anionic polymerization of ^ -lactams, as well as 'a new polymerization initiator suitable for it'; Furthermore, the invention aims to create a novel process for the monomer casting of u> - lactams.

According to the invention a method of making polyamides is provided in which one tu-lactams with at least 4 carbon atoms within the Ηίηχβ in the presence a basic catalyst and a compound - With at least one of the atomic groups given below in the molecule - '

polymerized

8SSB4V / 1S1

- '- 18454-38

Compounds containing at least one atomic group of the structure given above, namely

P-N-- (I)

are commonly referred to as phosphinimines. ^ and in the compounds used according to the invention can the remaining valence bonds on the phosphorus atom (P) and at the nitrogen atom OO in this formula to any inorganic ones or organic groups that have no active hydrogen contain atoms, be bound

The phosphinimines used according to the invention can also from dimeric compounds or compounds from higher levels Molecular weight consists of the 4 atomic group of the above given formula (I) repeated several times, accordingly of the formula (II) below

Here, a is a positive integer of at least 2 means and be the phosphinimines k% ns® & eötwed ^ ai ^ ine or einö cjGliische ferbin4uüg "- ölbgtoJUsk gm .hohem Molekülargowicht as Eealctionsinioiator are effective, their solubility in einemu) lactam, and usually poor in the polymer. Hence, i'm looking at

BADORlGfNAL

- 5 ■ - ■ -. "■ ■

the quality of the molded article from the polymer, if a phosphinimine of high. Molecular weight used should be, it is expedient and advantageous to adequate treatment to homogenize the phosphinimlnnj-lactam system apply.

Those used as mixed catalysts according to the invention Phosphinimines, in particular the compounds represented by the formula below

(—P "ft _} - - ■ (in)

in which E “and E _{0 can be the} same or different, and each EalogenatOBQ E-0 groups, SS groups or - IK

where R and E ¹ are the same or different aromatic or aliphatic hydrogen groups containing no active hydrogen atoms, and η is a positive integer from 1 to 600, are produced relatively easily and are useful as analyzers

Examples of as Kishkafalyaators According to "the invention useful phosphinimines are as follows

009: 844 / T6f

- 6 - ■ ■ ■ ■ -

N-LIe thy ltrichlorophosphinimine

ϊ _ν - N β

(2) if-Phsny It ric iilorphosphiniiaia

\, - η »PCI,

(3) 2r- (2,4-Dinitrophenyl) trichlorophosphine imine

IiO ₂ -V- V- N- PCl ₂ . K-Bonzoyltrichlorophosphiniiain

, - V- C-E = PCI,

(5) KM et hy 1-P- (phenoxy) -aiclalorphosphiniiai2i CH _x - IT - P (-0- <\> Cl,

(6) K-PhQnyl-P- (di) iethoxy) -iaonochlorophosphinimine

-ζ \ - Ii - P (OCH ₃ ) ₂ C1

(7) H-3enzoyl-P- (dimethylaiaino) dichlorophosphine imine

y \ - CO-NP

S44 / V6 7 8 ■ · "■ '

■ '' BATH

(8) K-Bonzoyl-tri-CcaproIactimino ^ -phoQpiiinimia

(9) K-Benzoyltripaenoxyph.pspi] Liiiiiaiii

. go - ii =? - (o-

(10) 1 -To ti-aciil02? Phosph, oraziy 1-2,2-diclilor-ii-, 4,4-trichlordiph.ospkaza-1 »3-diea

Cl

Cl ₃ P- »* P - H - PCl ^.

Cl

(11) 2.2.4 ₁ 4.6 _t 6-Haxaclilor-i, 3.5 »2» 4 _t 6-triazatripiiosp> orin (Phoaphoattrilcialorid-fiimoreo).

• ■ ■ v ^ci

Cl - P t * 01

(12) 2 _t 2 ^ _f ^ * 6,6 * Stex ^ bütö3 <y ^ 1 »5

Bu. OBu

4/111 f BAD

(13) 2,2,4,4-, 6,6-eexaphenoxy-i »3,5» 2,4,6-triazatrlphophorine

OPh OPa

PhO - P. .P- OPh

ί - ■ ·

OPh OPh.

2.4 _l 6-Trichior-a, 4 _l 6-tri- (dimothylamino) -1,3,5 * 2,4-, 6-triazatriphoephorin ₍

Cl - P. P-Cl

(15) 2,2,4,4,6,6-hexathiophenoxy-1,3,5,2,4,6-fcriazatriphosphorine

_{χ / O} Ph .- ·.

PhS - P. E-Sih

0984A / 167

(16) Phösphonitrilchlöri & - (retramöröG

Cl

P β
Cl.

Ol 7) Phoöphonitrilchlorid-Pol; meri3at

Cl '■. ;
- £ ~ P »Ν —-} -

Gl 'η »

The above-mentioned compounds and the process for their preparation are known. This phosphine imine compounds can be obtained by implementing a primary

> - · ■ Amino compound uder an acid araid with Phoaphorpenta- · chloride to form a phosphonitrile chloride compound and further implement this connection with an active Hydrogen-containing compound, e.g. an alcohol » Phenol, thioalcohol or thiophenols a secondary amine and "a tv-lactam.

The compound "of the formula (III) given above can also be carried out by ring-opening polymerization of a phosphonitrile chloride trimer or depolymerization of the highly polymeric product thus obtained or by reaction of the resultant highly polymeric product with the above-described » compounds containing active hydrogen will.

Examples of 'the boi the method according to the invention to-Latt ame iait at least applied 4 carbon atoms in the ring are pyrrolidone, piperidone, ^ -Caprolactam, Oenantholaotam, Gaprylolactam, Laurolactam and their "- mixtures

The basic catalyst used in process f; em . of the invention of any of the known ones used for this purpose Catalysts are used. Suitable eases are those which are strong enough to form with a lactam of an iminium salt of lactam that is easy to react by the formula below

can be represented, in which U. represents a cation, in particular a JÜetallkation, ·

Such bases include the alkali metal ^ alkaline earth metals and hydroxides, hydrides, oxides, carbonates, alcoholates, alkyls, "aryls and amides of alkali metals or alkaline earth metals. These basic catalysts have typically been sourced in amounts within the range of 0.1-10% used on diei / # - lactams. In the case of the pemaß According to the invention, the above-described phosphinimine compounds are used in amounts within the range of 0.02. to 5 mol%, based on the ^ -lactams that polymerized should be used · ν.

■ .. ■ '·. 003844/167 8. . ".» Ρ «« »times"

For the production of a polyamide by the method gexaäß of the invention is first carried out by a "basic catalyst" Heating together with a lactam to be polymerized melted. This way it becomes the basic catalyst dissolved in the lactam and reacted, being an iminium salt of alkali metals or Erdalaklimotallo is formed. This reaction leads to the formation of the iminium salt of lactam can within the temperature range of above the melting point · » points of the "lactams, but below the melting point of the polyamide to be manufactured. The time required for the reaction depends on the type and the amount of basic used Catalyst and the reaction temperature usually within the range of several minutes up to several hours. Dievu lactams and the basic catalysts, which are used in the method according to the invention should preferably be anhydrous leg. The implementation is normally carried out under reduced pressure and / or while bubbling nitrogen or other inert gases through it carried out by the melted lactams. ■

To the lactam, which is an iminium salt thus produced Contains alkali or alkaline earth metal, the above-described phosphinimine compound is directly or after dissolving in more lactam added to the polymerization reaction

009S44 / 1678

to effect. This polymerization reaction is advantageously and expediently carried out within the temperature range from above the melting point of the lactam and below the melting point of the polyamide to be produced, preferably from 120 to 170 ^° C. The required reaction time varies depending on the type of basic catalyst used and the one used Phosphinimine compound usually within the range of several minutes to several hours. In the process according to the invention it is also possible to use a known mixed catalyst together with the basic catalyst and the phosphinimine compound. Various types of additives, e.g. colorants, fillers, reinforcing agents, antioxidants, swelling agents, plasticizers, crosslinking agents and other stabilizers, can also be mixed in. Glass fibers, asbestos, graphite, molybdenum disulfide and natural, synthetic and semi-synthetic fibers can be used as reinforcing agents. . ·

When the polymerisation reaction of ω- lactams is carried out in practice in the presence of a basic catalyst and a phosphinimine compound, the polymerisation proceeds relatively slowly, previously with conventional methods. Accordingly, timing from the start to the completion of the polymerization is very easy; it is possible to dip the length of time during which the

0Ό9844 / 1Β78 ',

'1645638

the

i »

jait ^ g

miss 4 © |? iSifinduias # € lmeitß $ dlö

ips | igt the

with

to obtain. It is unlikely that sciirumpungsh.ohl · 3? Iiiume unä. other l'eiilep awiti'eiien · ', - "*

Vie ErfinduöS wiyd na ^ Esteilend based γοιχ Se $ spiölen näner erläiMbert _t in wel
the w -

For 3oi el 1

Sine mixture; φ & fQQ φ £ * ßap? Glaef am uiid 6 ρ | 2 _f § üpi- ^) would φ £ a öi |> ad % el -100 pinem v # r |? in © e ¥ ^; en | 3γρ «2 | 0 pa 1%) lintel li | ücc

by means of ^ iiieie Kapillaaeo "-during 2 '

4er

ala Willstellslauter der PliessfreiJieit '(? a <3 * -fls> V7 t (which den -Äeitabseluaiti; aacii Zusata de # Mi' bcaeht, which is tar required, vm. visibility in the olymmerization mass to © rb.Glteji | go 4ass the meniscus remains undisturbed if the actuator is tilted at an angle of about 4-5 °), 1% in 5½ minutes was completely solidified and held or detached from the wall of the actuator due to contraction or deformation (this period of time nash addition 4es l & oeliteatalyeattMPS which is necessary for reaching this state of 4ei? tionsiaasse wir4 _f 'is nasiisteÄiend as a duration% ö »ei ^ imet) * Is was a natogu laeißos unä sütoes ijerisat in

BATH

Example 2 .

5> 1 β (O »^ 5 toi!) £ -Caprolactaia wurden.bei heated 80 ⁰ C for 2 hours, to which 0.73 g (3% pick-up) Natriümaetho: £ were added yd * Bio temperature was raised in 28 minutes raised to 160 ⁰ C * (25 mole percent ° ") Phosphonitrilchloridtrimeres to the above mixture 0.393 g was added and polymerization was carried out C at 160 ^0th, lisch 10 minutes dio solution not xaeifh flowable and the solidification time betrue 16 minutes · '

If the .Pölymerisationstemperatur was 13Q ⁰ G, was the Einstelldauar the Jließfreiheit (no-flow time) 39.Minuten and Verfestisunisszeit was 46 Hinuten.

Example 3

A Uischuns from 500 g £ «-Caprols.otaa \ md 7.41 g (3.0 UoI- ^ j) Kaliuiahydroxyd were to 100 ⁰ G on an oil bath under a reduced pressure (3 aaa Hg) and unaffected. Heated through nitrogen gas for 2 hours. Subsequently dio ^ temperature of the oil bath was raised to 110 ⁰ C, abaudestillieren uza a very gerinrö amount of f-caprolactam. Thereafter, 1.54 ε (0.1 MOI ^) Phosphonitrilchldrid-Trimereo eceben zuf ^ and the temperature of the oil bath wurdo increased to 15O ⁰ C and the mixture was heated in a nitrogen atmosphere. A white, viscous polyamide was obtained in almost quantitative yield. The installation time for freedom from flow was 19 minutes and the solidification time was 22 minutes.

0 0 9 8 4 4/18 78 'BAD

-16- '16A5A98

·· Game 4 ■

Sine 2II research of 500 g of caprolactam and 6.2 g of I ( "# 2.5 föol-) Kaliunhydroxyd was heated at 100 ⁰ O in an oil bath under reduced pressure (3 mm Hg) while passing through! Stickstoffsas for 2 hours .

The temperature of the oil bath was then increased to IfO ⁰ O to. a very small amount of oaprolactan had to be distilled off, then 2.08 g (0.2 mol%) of phosphonitrile chloride triineres were added. The temperature of the oil bath was brought to 15 °° 0 and the mixture was heated in a Sticketoff atmosphere. An almost white, tough polymer was obtained in almost quantitative yield. The setting time for the flow-free state was 15 minutes and the solidification time was 19 minutes. ; · '..' ·

Example% '

Then 56.5 g of aiaiaoniuni chloride and 200 g of phosphorus pentachloride According to the usual procedure in 500 g Tetrachloroethane for 7 hours and 30 minutes under reflux the excess ammonium chloride was kept filtered off and the tetrachloroethane was reduced under Pressure distilled off. The residue was removed with benzene * traded, 100 g of the reaction product were obtained, which was obtained from a mixture of 55 E ^ hosphonitriichlorid-Triaeres ^ 10 g of tetramereo, 30 g of other cyclic polymers and 5 g of a straight-chain polymer consisted of

009844/1678 * ■ _.

ORIGINAL BATHROOM

from $ Q &. & £ ^ -o pBOlaotifiaa vm & S ₉ Z

was in a 100% oil bath under a reduced brackish {5 -vm. Hg) and "ö &ter" Bsireöleitea. voa Stiekst & fT— gas '"»' honoring 2 booths heated? ·

JlnseM.i eSend was the oieinrrer-atur of the oil bath araf ^σ zmr AhasstlHaticu a seke serisgea liease des ^ - toas g; esteifert »BaBack was a 3> GS g'des vo-rs-tOiiead sciir-ie'ben.eaRDaktio-ikspio-ikspio-ikspio odukijes aiigegeieii and that of the oil bath brewed at 15 ° C - Brtci clas Gemisefe. la elaer S.tiok— stoiTatmospaSre .erMtzt "It would eia-uaAeaa white Po-Iymeri" in almost qualitative "yield © rlil3Lte" i "Bie ^ <2 admission cheat 28 Uinsitea tmd die

51 ^

.Example. 6> .

A Miscliimg · aöf-56 · »^ E £ -Gaprolaataa mid 0-> 6 g (5 KoI- '·

IXatriiiiabyclroxyd were.-ia aiulyftfead at about 1GO ⁰ O-mater a reduced a bridge C® _t 5 to 5 asa-Hg) tmd under Surciileiten. vöü nitrogen gas for 2 hours, 'heated. ÜJuroa Stsigerimg der SfeaiperattEfdes IiifBiatiestiiir bath) on 12ö ° G. A very small amount of the £ -0aprolactam3 was distilled off. the atmospheric Bruek Äürixclvsebracat became »the air temperature of the air bath was 130 ⁰ O eroöät. uad O ₉ ZB g (0 _t 15.: mol%) Hiöspaoaitrilehlorid-frimerea were jsuseetat tmd uniformly dissolved »© ie fcliscauag VAirdö ia a Stiekataff-

"box 1> O ° 0- erMfefc * Eis mirä® © in white © sat craalteau Me ££» sfcel £ e & «uer ^> der- Flleßfreikeit; imä die Vcrrestlgsrnssäaiies · 'v / a * · die Po-lyEeri &aiiiiansteaparauiEramf' 17 ' Q ^ O ¹

_t "botrpg äi @ EinstelMaiisr eier ö? liöEfir @ iiteit, 9 and öiro Veriestigan ^ sdaHQX * '5ft iü

example

An illachiinr; aÜ3 5QQ gi ^ nröüdoa imd 20 g (S _t i> Κο was on SG ⁰ U in. one, üioad \ mter a bridge (> inßi Hs) and under 'Atirciileitea vc & StLck «v / during 20 liinutea eritzt * Daaaeh was the temperature of the oil bath allmiöiliclt zuYAtodes-tillaticm bucket · eb & · low iien ^ e ^ i νοη Deia yrrolidois. geateiQesffc · to the Aich ER- geboadea mixture, 6 g _t 2 * 5 Coe Üal- / 0 Phospkotmit-rIL-ciilorxd Triiseres zurjegeOstt und di © LCicebaiBs: wiardö "bei ■ fcesiperatur st ^ GJiongelaoseJi» You üijaötellüaiier * der · Lgit was S Kinutea ϊίηά the iferieGuigaBG's.datiier 'Ί5 Kacä,. 15 Stuadea'& iefe. was made with polymerisat; kociiendeie VTasser zwöiExal ^ sometimes ge

. · Es »vurdea> 7ö S C- ^ usbotttö? 4-? Ί) eiaoa. Totally fcäadig Pol, ymerisats received. Bie grundjaoelar © Tiskosit-ät = of the polymer! Gate », gladly seen in ia-iCresol ibel 2 ^ ⁰ C _β cheating .1 * 8»

_B ÄD

Examples

8 to 10

The procedure described in Example 1 "vmrdo with dor amendment repeats that instead of i-sodium ethoxide the oil-terminating compounds when the polymerization is carried out VJ-vendot wurdon. The results obtained are listed below

fieiiipiel

link

0.36 s KaE

. Einütell-

dahor of verfe- color

Flow 3 tides

_S_i? S ^ nunKfl- Polyno-

slacker
(nin.

ricatc

White

1.35 p

(1 ₁ 5

0.48 s BuLi (1.5 ^ ol-%

Example 11

21

43

32

67

White

The procedure described in Example 1 was carried out using 1,566 g (5 Hol) ^ -Caprolactaia, 4.06 g (1.524bl-5S) x7atriuii_othoxyd and 5/6 g HoS ₂ as filler and the Iiischun ^ subject to polymerization. The flow-free setting time was 58 minutes and the solidification time was 81 minutes. In the polymer obtained, the filler was uniformly dispersed and there were no internal defects in the polymer .

1845498

Mixture of |> ÖÖ £ j C * -

a reduced pressure C3 nueä Sg) lind

s wähfreiid 2 B-bundeii Erkit £ i% i woiiauf tie

dos Ölbads eu £ 1Ί0 ⁰ 0 fctir Äbdöat; iIlG.% iGii «iüer öeto« on ^ e des GaproXactamä erhokt Vüuirde *. I2m tier aicii den iiiskung. wurdoa ^ * ö g (Ö | 3 ^ Mol * · ^ 5 ^ 2i4 _% ^

iir dea oil baths siurde auJP 15Ö ^Ö C gokcacki; üM -dlö lliäei

lii a S ^ iGkBtdffafcrdoapkiiro wälirößil B% uaditn Taafäalteüe Polymarlöat was v / elü »_; , ·

WuMi

ti-Il ftpde eil löi
Yield constant. The setting time of the FließfröilxGit

carried 55 meows, and the solidification time was 2 hours »

When the polymerization was carried out according to the procedure described in Example 1, 5 »5 g (0.0487 mol") £ -gaprolactam, 0.079 "β (3rd MoI-SO Matiiuauaethoacyd, and 0 _B 07-2 g (0 "201 Mol- #) 2.2 _§ 4,4,6,6 ~ He2 £ athlophenoxy-1,3,512,4,6 ^ triaaafcriphospliorin used". The duration of the ^{1 1} meal-free acit "was 30 minutes and the defection time was 57 Minutes _a The received no polymer was-white- ·

When using 0.0443 g (0.115- ^ 01- / 0 of the mentioned 2 _& 2 "4 ₃ 4, .6-, 6" Hexathiophenoxy-1, 3> 512,4,6-triazatriphosphorine "was the setting time ' the freedom from plucking 40 minutes and the TörfestigungsEoit 49 minutes, whereby the 'obtained polymer was white' * · - -' ■ ■ -,. "..

When carrying out the polymerization according to the method described in Example ft were 5 * 5 g (, 0487 mol) ι -öaprolaotam »0.079 g (3 mol%) ITatriummethojcyd and 0.049 S (Ο ·, · 393" Kol ~ / j ) K ^ BönzOyltrichlorphosphiniiain used. The infiltration time of the flow-free was 41 minutes and the solidification time 46 minutes "A white polymer!""Sat" was obtained. ■. . '"'■. ■ · ■

, V

00.984 ^ / 1678;

Seisp_iol 16

When the polymerization was carried out according to the procedure described in Example 1, 5 S (0.0442 mol) t -caprolQCtoa, 0.0706 g (2.86 eIol "^) EaIiumhydroxyd and 0.023 S (0.157 ϊ · 'o1-ν <τ) IT-Iviothyltrichlorphospainimin-Iiimores used »Pie setting time of the flow. Freedom, was -15 minutes and -the solidification time 22 minutes · -It was a. t · v.eißea Polymeri.sat obtained. '

When using Ö ₉ O16 g (0.109 ίίοϊ - ', Ό of the above-mentioned' Pliospainiain ', the setting time of the I? .Freieiaeit was 20 minutes and the pre-setting time 34 minutes, whereby a v; oissos polymer was obtained *

Example 17

ill 11 III »lMlHll j I. IHHTlIlMIfIl ΙΠίΙ I ifTTTr-mfTlT

In carrying out the polymerization according to dor dor in BOI game 1 beech rubbed Arbeitsvieiae, 5 S, (0, Ο · Ί4-2- koi) ^ -Gaprolaotam "0,07W g (2.85 Mo 1-9S) Kaltumhydroxyd and '0 .02 s (0.1 mol%) IJ-Hienyltrichlorplio ^ pliIaiaiain-Diaeres · ends · 'The setting time for the freedom of movement was 22 minutes and the solidification; sseit was 33 ^ iiiutoiia It became a white polymer , get on. "'■

When using 0.04 g (0 _? = ..! ". ·

1678 ',

BATH ORIGINAL

16.4 5438

• "At" execution of the PolyEierisatioa. after, the, la. Example Ί bonchrieboncu Terfalireä wurcba 3 £ "(0 * 0432 οο3 $. f ^ apra lac tarn 0 * 0715 S O Kol-%) ITatriumsae.t & öKyä tuid 0 _% 02 g - '(Q% 1 4iol «? 5) l: i-4- ^ enyli ^> ricixlorpiiöspliiaimiß. *» IDiiaQr (iB Vo3? Wondo% * Öiö Einst eildaucjr der Flieüfroikeit v / ax * 23 Ktautcii tiiid diö i duration was 32 iünutoa * Ss wui ^ d © © in viöissöii th »

Bei- VeJtocndu & g voa Ο ^ Οή g (0 »ä ^

piiiiiaiavcröißä \ i3ag was the setting wall »d © 3? Fl 20 wilauten Uiid dlö VerfostigunGssceit * & »Äiautnat -Das PolyniGäPir & t« ar

Eöi Ausir-hruns der

luggage dei * £ &

0 ^ 22 g

«Rliöitßv, -oiee v / urd ^ fa.
sb UM Q

irVeftdet * Öef * Eiü5% §iMauer der ^

Umh- ^ drVolliät ^ Miig ^ l the

\ vüi? dö © ■ üL- ^ Ql ^ fiäs ^ isat iÄ ei-nöi Auebeiibo f

Dio grundaolure Vielioüi-iiät deo Polj'iaeriQato, measured in

Hfl

_BATH

^ i game

The procedure described in Example 15 was repeated with the modification that instead of = ii-Bonzo7 / ltrichlorpaosphiniain 0.0419 G (0.195 iiol- #) of I-Tetraohlor piio5plioranyl-2 _% 2 ~ di_chlcijc ^| - ^ * 't4 _f 4--1irjchlor'-diphoflplia2a- ^> 1 »3-dien were used. The Einatclldauei ^one of Pließfroikoit contributed 75 "inutes'and""" Yerf estiEuniisdauoa 95. Kinuten · G was η hellbrounos polymer;? Obtain.

l 21 "'

When the polymerization takes place, the In Example 1 betchriöbei-ion Arbeitsvveico iv were 51 S, f-Oaprolactam, O _t 73 O ^ ol- &) NatriuEuneth.oxyd and 0.375 S (0.18 mol%) Phosphiio-Nitrilchlorid-IetraiiGros werwondot The flow rate was 48 minutes and the solidification time was 53 minutes. A light yellow Polviaeriaat was obtained "

Example 22

The work described in Example 15 v; urdo ait the amendment repeats that instead of 2T-benzoyl tri ~ Chlorplioophiniiiaat 0.050 g of plioophonitrile chloride polymer (η »554) were used was 41 if-U-slots and the time to mute was Kminutes. Eo a white polymer was obtained · ·

BATH ORIGINAL

184 5498

polymer. w $ g§® Ta & ispieJt & vsreisQs ^ © mai- dies * io & e-

became

woteei

faxbloses

E C

approximately

ei soaps -ye ^ iiigisrten Ecuiefc (Q ₃ ^

¥ on Sticksfeoffga ^. feieidursb. whereupon the iesiperatur des, Iiiif
in the © ine very small amount

2 'p

Gradually pressure with, ElIfe-.iroa nitrogen gas

dos air baths to Ί%)? ^! @, e ^ ö & b- u®ä 2§3 g ^ ΟγΊ! Ptiosplioaita? IlGiiloriä *>! Rrime3? Es · were given to the G-emiseb. gleieliföxmls ■ solved file entire Mis @ 2ii * ng w.ur & e ia a gotronata GieBfoim poured »Me Sinstelldauar dor yiioßireilieit? b & wore © Q Hiautea omd the since vjar-80; Siijatttoaa * 5as emsougta

.,. ■■

009 ^: 844 / 167-8

78 4 54 ^ 8

oiriea Ultraaoliallreflelito.akapo ^ at

ülXL SuoiilcoribaiCteleineiXt; with the test material ± a was brought * a polyriorisate; aiir "Iimenfeiiler

faur-sne g checked (Dafeei νμ ^ ςΐ © «£ ol £ <m <le ^

dot5; Pre ^ vianz: * i KQj; liapUiiavfölleitforiat ieipnlo-iva

4i A ¥ taai; .Yq _: r4öfe? An ϊ linear g. 400? Kerta (a /) j.) ,, Daba.i

noqii. iiinero. Error iix do-m ferfei ^ gAat ^ lXttn and ™ Polymer! Oat filled ^ Daa Pftlyiaeyiaa.t was homosaii

Dio ralatiTo "viscosity of the polymer © was T ₉ Q ₉ gomes-- ' ^a in alaer LboLing of 0", ö g ö

Düö Produlct owned the
Bl ^ enachafben · - 'Unit

'! ■■ ι ί'<ιίίΐι ι ^ ι ι I Hl I m | ι || ¹ H ΓΙ »KMJ" I ~. ΜΒΜΜρΜΜ ^ »ΡίΙι1Μ""ΙΙ1ΙΡ— ^ ί_

20th

2750.Q

'ω »

Score.

Heat consumption temperature

.18.5 kg / om ^& .0

4.6 kg / cm ² '■ _ - ⁰ G

Durohaohlagsfestigksit '"^ f-ToI t / ja®. 56- .- ■; ..

Dielectric constant © 10 -Gps. "5.7. \ ■

* t -

Loistungafaktoyg (Yerluotwink & l ^ 10 Grandpa "0;» 00 · 5

Specific resistance ■■ '... "Xi." ^: · | § χ ^ o ^^

009844/1678 _BAD

16 A 5 4 9 8

Control 1 . ,. ■

Bine Kiachung auö 5.5 £ £ - -Caprolaotam and 0.058 g (3 col- $) of ifatriunhydroxyd were in an oil bath at about 115 ° Q under a reduced pressure of about 1 now Hg and under dur ohle it on from Stolcatoffgaa for 2, heated for 5 hours whereupon the temperature _t dea oil bath to 125 ° C Eur Abdootil3utlon a oohr

In a Verouoharolxr (Reaüenzßlaa), dao a Kiachkatalyoator contained ■ maintaining the <f-Caprolaotaialöaung under einor .. St-lokßtoffatirdophiii-e Gegoeoen and Gleiohföriaig so GeaiocM. "Di ο \ bn>" at 150 ⁰ Q *.

Mon ^ a deo ^ -Cnprolactano increased

Einstölldauor the

^ freedom of use and the period of availability for each of the used Kiü. 'Hlaitalyöators were the' "following

On-off

Miacnkatalyeator Ge \ /. deo MoI- ^ otoll- fest! - Walking

Kiochkata- Kiachlcata- duration gun ja- dos lyaatora lysator of the "dahar poly— (lay). ? lie2r (a.) neri-

froi- aata he it

Phosphorus tr
chloride 24 0 * 360- 15th 22nd yellow Phocphorpenta-
chloride 0.296 16 20th orange Jho-sphoroxy "
chloride 25th 0.346 18th 21 we 13 NA ce tylcapro-
lactam 11th 0.146 < 3 30th White

OQ9844 / 167 8

Control 2 ',

A Misohung of 240 g £ ~ caprolactam and 3.24 β O "5 MoI Jy) was Hätriummethoxyd / at about 10O ⁰ C under a comparable rings rtenDruok (0.5" to 3 mm Hg) while held for 2 hours to absudestillieren finally a very small amount dea <f-caprolactam. Thereafter, the temperature was raised to 150 ⁰ C,

while the pressure with Stiokstoffgaa back to atmospheric- '. pressure was brought. A solution A was obtained here «

In addition, another 240 g of cL-Caprolaotam "were used at otv / a j

IQO ⁰ G under a reduced pressure (0.5-3 now Hg) during;

Held for 2 hours, whereupon as Ko- or Miaohkatalyiijator i

4-, 36 g (0.7 HoI- ^ y N-A-oetylcaprolactam added and equal- '

were loosened in a shape. Thereafter, the temperature was gastoigort to 150 ⁰ C. The solution obtained in this way was referred to as solution B.

Solutions A and B were uniformly

vascular mixed and immediately poured into a separate mold, which was heated to 150 ⁰ C. The polymerization took place immediately when solution A was mixed with solution B, the solidification time being 5 minutes and 40 seconds.

As a result, air bubbles could appear during the stirring mixed into the kicch vessel, not removed will. Inside the grit pipe, the polymer was solidified,

Q 0 9 8 L t, [ 1 6 7 8 -

. . .1645-49

, .which made pouring difficult and the liquid remained ^: polymerized and solidified back in the mixing vessel,!. making further stirring impossible. When exam

> - the polymer produced with an ultrasound reflector

■. ι

. It was found that the polymer! aate had the disadvantage of a considerable number of voids. When used
a Mlsohkatalysators for a rapid polymerization, eg
of N-Acetyloaprolaotam, it is necessary for the mixing of the 'Jösung A and Solution B and the defoaming and pouring i ,, the His-hung, within a short period of time auszuf Uh ren " · · ■ '- ..'

When adding N-Aoetyloaprolaotam but solution A without I mixing solution A with solution B, the drop continued
of li-aootyloaprolaotam directly initiates the polymerization
and uniform mixing became more difficult · ..;

/ 1678

Claims (1)

Claims 1. Process for the production of polyamides by polymerizing one or more ti -lactams with at least 4 carbon atoms within the ringa in the presence of a "basic catalyst and a mixed catalystB, thereby characterized in that the Miaohkatalyeator is a Phosphinimi-nverbindungen with at least one atomic group of the formula below Used in which the remaining valence bonds of the phosphorus atom (P) and nitrogen atom (N) are bound to inorganic or organic groups free of active hydrogen atoms. " ⁼ . 2, method according to claim 1, characterized in that c - the Kisch catalyst is a straight-chain or oyolic one Compound used having the atomic group given below ■ i- Ϊ in which the remaining vales. bindings injected indicatedon way bound bind and η a positive integer of, 2 bio 600 represents. - 009844/1678 ■ 16 4 ^r 4 9 8 - 31 - 3. Ancestors according to claim 1 or 2, characterized in that that one al ο Kieohkatalyeator a straight odor oyoliecho Compound used which has the following atomic group contains, in which the grids R ₁ and Ep equal odor ver. Ochioden oein can and each a KalogQnatoia _{t represent} an IiO-, RS- odor -Ii 'group, where R and R' the same \ r · odor are different and aromatic or aliphaticohe, Carbon groups free from active pollutants mean, and η is an integer from 1 to 600, A, method according to claim 1, characterized in that zaan ala MisohkatalyGator inobee special Phoophonitrilohlorid-Trimö ros used, ■ "■ - ■"" 5. Ancestors according to one of claims 1 to 4, characterized in that san the basic catalyst in a conge of 0.1 bio 10 Ko 1 ~ £, based on the 2 "-Laotaxa _r and as the Mischlcatalyßator / Phosphiniminverbindungen in einor Kinge 0 _t P 02 bia Kol-5e, besogen the £ _-lactam used S. Ancestors naoh one, the claims 1 to 5, daduroh gekennsöiolinoug da3 can carry out the polynoriaation in oinor SOiia, '■ ·, ■■ .-: ■ % μ ORIGINAL 009 8 /, 4/1 S78. ;,