JPS5821425A - Manufacture of nylon block polymer - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to (1) acid noride functional materials derived from acid halides having human-xyl-containing cosmoid and cybaride functionality or multihalide functionality; (2) the corresponding acyllactams. 11 Processes for functional derivatives and (3) nylon block polymers and corresponding nylon block polymers using such functional materials.

Polymers containing polyamide segments and segments of other qualities have been disclosed in the art and are hereinafter referred to as "nylon block polymers." The combination of polyamide segments and other polymeric segments makes it possible, among other things, to obtain block polymers with unique combinations of properties.

These properties can be altered by changing the polyand and/or other polymeric segments in the block polymer. It has been found that such block polymers are suitable for bone use as fibers, fabrics, films and molding resins.

U.S. Patent No. 4051164 and U.S. Patent No. 4.224112, both by Messrs. H@1rick and Gabb@rt.
Each of these patents teaches nylon block polymers containing nylon segments derived from lactam monomers and polymeric blocks derived from polyols. ) I@drick si- and Gabb@
In the nylon block polymer taught by Messrs. Rt., the polyacyllactam provides the linkage for the block. Molded articles having a unique combination of properties can be produced from the polymers with a unique combination of properties taught therein.

The above-mentioned US El patent teaches the preparation of block polymers consisting of KI11 polymerization of lactam monomers, polyols, lactam polymerization catalysts, and polyacyl lactams together.

U.S. Reissued Patent No. 3M7 for the production of nylon block polymers by Messrs. H@driek and ()abb@rt
The contacting method for ikendo-alcohol incorporation as taught in No. 1 may be used.

US sIF# permit No. 1657.385 1ji 1181
K + x, M Block polymers made from polyethers are disclosed. Certain polyarylene polyether initiators disclosed as useful have terminal groups selected from the various specified groups.

Alternative methods for the production of nylon block polymers of the type taught, for example, in the Hadrick and Gabb@rt Visit patents mentioned above will be of interest to those skilled in the art and are an object of the present invention. It is. Another object of the present invention is to provide new materials useful as intermediates for making nylon block polymers.

These and other objects will become apparent from the detailed description below.

According to the present invention, a lactam monomer, a basic lactam polymerization catalyst and a lactam monomer of the formula R is a divalent or polyvalent group selected from a hydrocarbon group and an ether bond-containing hydrocarbon group, and 2 is (1) a minimum molecular weight of 2,000
or (2) a minimum molecular weight of about 2,
a polyester segment containing a polyether segment having 000 and the nylon plastic thus obtained. A polymer is provided.

Also included are materials in which 2 is a segment of either a hydrocarbon or a polysiloxane.

The acid halide-containing substances referred to herein include two or more hydroxyl-containing groups (i.e., Is Q groups, C
- It can be produced by reacting with a fist-hydride functional substance containing. During the reaction mixture, the amount of acid halide groups should be maintained in excess over hydroxyl groups. In this reaction, the acid halide material is attached to the human tetraxyl position in the hydroxyl-containing material through an ester bond.

Hydrogen halobide is produced as a by-product from the substituted hydrogen and halogen. One example of this reaction may be written as: 1 nR'+0H)z +mR+c-X)y4@halide 1
Intelligence + anal (my-nx + 2) In the above reaction, there are 2 R'+0H)x! substances containing at least more hydroxyl groups, ie X is at least 2, preferably 2-4. This material can be a diol, triol or even a material with a higher hydroxyl content. The group R' in the hydroxyl-containing material can be a hydrocarbon group (preferably having a molecular weight of at least 100), a polyether group or a polysimixane group.

Unless otherwise specified in I#, the polymers referred to herein are
or "molecular weight" with respect to polymerized segments, as determined by methods well known in the art, such as by Y phase chromatography. 111 means the number average molecular weight that can be determined.

As used herein, the term "polysiloxane" refers to a group or an entire segment having the structure: one or more repeating units of +91-0 units (units per square meter) containing at least 50 by weight -
means a group or segment containing

In the above structure for the tetraquinane unit, mu can be methyl or phenyl.

The polysiloxane groups or segments typically have another group present, such as an ether group with a lower alkyl residue such as an ethane group, where such ether group is typically a repeating cytequinane unit. It is a base that has a tangled end on steel.

Another such group is a 50% polysiloxane group,
Preferably, it can be less than 30% by weight.

Wild R' groups are hydrocarbon groups and polyether groups. Examples of hydrocarbon radicals include alkylene in the case of diols such as ethylene glycol, and macromolecules such as segments of polybutadiene which can be functionalized to contain two or more hydroxyl groups. True north hydrogen can be given.

A pyrene segment in polio which can be functionalized to contain 211 or more hydroxyl groups is one example of a polyether group.

Examples of hydroxyl-containing materials useful in the reaction include, for example, ethylene glycol, bicarbonate glycol, poly(oxybutylene) glycol, oxyethylene glycol, poly(oxyethylene) diol,
Poly(olopyrene tetrol, polybutadiene diol, hydrosilyl-functionalized polydimethylsilol)
Nans and combinations thereof can be used, such as block polymers of poly(oxybutylene) and poly(oxyethylene) functionalized with two or more hydroxyl groups.

That is, it contains groups in which y is 1 or more, generally 2.3 or 4, preferably 2.

The lambda group in the acid halide material is either a hydrocarbon group or an ether linkage (generally a hydrocarbon group containing up to 20 ether oxygen atoms by weight).

Hydrocarbon groups are preferred, but those having 1 to 12 carbon atoms are most preferred; even more wild R groups are RK
A hydrocarbon group or an ether-linked fully blind hydrogen group providing at least three consecutively bonded element atoms between any two bonded carbonyl groups. Examples of preferred acid halides include sebacic acid chloride and phthalic acid chloride in which the carbonyl group is attached in either the meta or para position, i.e. inphthalyl acid chloride and terephthalyl acid chloride, respectively. can.

In the above structure, X is halogen.

In yet another aspect of the teachings herein, the reaction! In place of the acid halides listed as useful are acid halides or structures having the structure (where X has the above definition and R1 is an alkyl, aryl, alfurkyl, Phosphorus- or sulfur-containing acid hydrides can be used, which are l, alkyl, Φ, aryloxy or alfurkylo.

Examples of acid halides that can be used in the above reaction include adipoyl chloride, taloyl chloride, trimene chloride, trimellityl chloride, oxalyl chloride, yl chloride, biromellitoyl chloride, and bimelyl chloride. Irkulotuide, glutaryl chloride, benzophenonetetracarboxylic acid tetralide, oxydiacetyl chloride, sulfuryl chloride, phosphorus oxychloride, cepacic acid v9ide, azefin acid tetralide,
Alkyl phosphonojiku four resorts, aryl phosphonojiku four resorts, aryl phosphonojiku four resorts, alkyl phosphonojiku four resorts, alkyl phosphonojiku four resorts, aryl phosphonojiku number resorts and alual 11? Ruhonuhonojiku kicking date can be given.

The numbers indicating the amount of functional groups for inclusion herein (eg the numbers x, ysI- and b above) are integers with respect to a single molecule of the substance. However, a large number of such substances! Polymeric materials are generally present in synthetic or footwear materials containing different amounts of functionalized species, with some species perhaps in higher or lower amounts than desired. The number indicating the amount of functional groups for such a mixture qlJ''t or m*f represents an average of the various species and therefore does not necessarily have to be an EI number. All hydroxyl groups e:! are converted in the 17J reaction. By providing an excess of acid halide groups over hydroxyl groups, the resulting reaction product is functionalized with acid halide groups.

The reaction is preferably carried out in the presence of a non-inhibitory solvent such as cyclohexane, toluene, dihydrofene or acetone to facilitate the removal of any hydrogen halide that may be formed. In addition, hydrogen halide can be heated,
Eliminate the presence of solvent by removing it by vacuum, nitrogen sweep, etc.
It is also possible to proceed with the reaction in a state where the reaction is still in progress. If a solvent is used during the reaction, basic materials can be used as a convenient means of removing hydrogen halides, acting as scavengers to produce by-products that are insoluble in the solvent. Well known acid scavengers can be used, such as acid scavengers. The reaction can be carried out under essentially ambient conditions and between 30° and 150°C.
will proceed even more rapidly at higher temperatures such as,
The exact temperature for this reaction can depend on the S medium used. If a solvent is used, it can be removed after the reaction by distillation.

The above operation is performed with a tetraxyl-containing human diaryl group.
lI! The reaction between the acid halide groups of the ^ride substance, ie the following WIl/-ride blind functionalization can be produced.

(1)) In the formula, X tX 7% EI If and & is 1
．． is an integer of 2 or 5, b is an integer of 2 or more, R is a divalent or polyvalent group selected from a hydrocarbon group and an ether-linked completely blind hydrocarbon group, and 2 is (1 ) polyester (this polyester is not solely composed of poly(tetramethylene terephthalate) or poly(tetramethylene inphthalate))
or (2) polyether, (3) carbonized ice or (4)
) Segment of polysiloxene.

The following halide-enabled materials, which represent other embodiments of the teachings herein, may also be prepared according to the procedures described above.

In the formula, R1 is an alkyl group, an aryl group, an aralkyl group, an alkyl group, an alkyl group, an aryloxy group, or an aruoxy group, and X and b have the above definitions. 2 is a segment of (1) polyester, (scented polyether (this polyether is probably not just polyarylene polyether))% (3) hydrocarbon, or (41 polysilokinane).

The above formula! ((transformation) and formula 1 (27) are the above-mentioned (1) polyether, (2) polynyf k
.

(8) a hydrocarbon or (4) a segment of the polycyct4nano27 segment for the reaction product JIEIII shown by formula 1(a) and formula 1(2), which is a segment of the It can be the same as the R/ group of the functional substance.Alternatively, the two segments are linked to the starting acid halide-containing residue.
It can be a segment containing two or more residues of the hydroxyl group.

Z-4 here! In keeping with the description of the dament and tX''R' groups, the description of the polymeric heptadment/group refers to the oligomeric segment/group unless the specific use excludes such an interpretation.
is understood to include groups. In addition, these sedament/groups may be linear, branched chain or jIlt (#tar
) structure.

The 2-segment polyester segment is a di^ride sensual box! It can be derived from the reaction of an acid halide with rutihalide functionality and a human xyl-containing material, in which the groups in the human xyl-containing material are linked together by the acid halides through polyester linkages. Examples of human gastric xyl-containing starting materials that can be used in such reactions include GX, such as ethylene glycol, boopylene glycol, polycarbonate diol and polycarbonate diol, and polybutadiene diol. It may be seen that acid halides such as those exemplified above may be used.If one looks at the formulas above, it will be seen that there are many types of polyester segments that can represent 2 in formula 1 and formula 1. In the embodiment represented by Formula 1(a)K, polyester segments consisting solely of poly(tetramethylene tereate) or poly(tetramethylene inphthalate) are excluded. Two segments that are polyester segments are actually , it should be noted that smaller segments in another category of possible z-segments, such as hydrocarbon segments or polyether segments, should be considered.One example is a segment of polyester. It can be derived from polyether group-containing hydrosol-containing and @halide substances, and
Two or more polyethers S become bonded together through ether linkages and by twig inclusions. This and the xyl-containing substances may be derived from diols, triols or polyols. Specific examples of such are poly(oxypropylene) triol and Tele7.
Reaction formation with thaloyclotide, in which the residue of the teryl chloride provides a single linkage between the two units derived from the triol. may be more particularly described as a poly(ether-ester) segment, which is a preferred polyester segment type within the teachings of the present invention. Similarly, other preferred polyester segments include diol segments containing polymeric hydrocarbon units. It is also a segment that is the reaction product of a nitriol with an acid halide, the 112 or more polymeric hydrocarbon units being bound together by the acid halide material. There are reaction products of dienediol and terephthalyl chloride, in which two or more polybutadiene segments are linked together by terephthaloyl chloride through a ether linkage.

The polyester segment, which may represent 2, can vary in size, but generally has a molecular weight of at least 500. The preferred molecular weight for these segments is about 't, ooo - about 25,000. The more preferred types of polyester segments or polyesters containing polymeric hydrocarbon segments generally have a polyester segment content of from about 500 to about 4. Go.

contains these segments with a molecular weight of .

Additionally, as discussed below, the nature of nylon block copolymers made from acid halide functionalized materials in which the %2 segments are polyesters is such that the polyesters have polyether segments with a minimum molecular weight of about 2,000. If it is present, unexpected results will occur.

The polyether segment is real! Two segments are preferred. Such segments may be derived from hydrosil-containing materials containing polyester segments. Examples of such preferred tetraxyl-containing materials include, for example, poly(oxyethylene glycol, poly(oxybutylene) glycol, poly(oxypropylene) diol, poly(oxybrobylene triol, and poly(oxypropylene)). Poly(oxypropylene)/poly(oxyethylene) functionalized with tetrol and two or more hydroxyl groups
Floc polymers can be mentioned.

The upper 1eZ polyether segment generally contains at least 50%
0, preferably at least too much and more preferably at least about 2,000. Preferred molecular weights are from about 1,000 to about 25,000, but less than 2,0
00-25. ODD is more preferred.

Even more preferred for diol derivatives is about 2
,000 to about 4,000, molecular weights of about 3,000 to about 12,000 for triol haze conductors and about 4.00.0 to about 10 for tetol derivatives.
It has a molecular weight of 0.00.

As will be described in more detail below, according to the present invention, the properties of a nylon block copolymer prepared from a functionalized material in which the two segments are polyethers are greatly influenced by the molecular weight of the segments. It has been determined that the preferred molecular weight of the scales and sills yields unexpectedly significant results.

Furthermore, it was confirmed that the minimum amount of cross-linking in the nylon block copolymer, which occurs when the composition of the acid halide blind material has an average anti-functionality of 2 or more, also results in unexpectedly improved properties. Ta. These features are discussed and illustrated more fully below.

formula! (In the embodiments represented by
0-muR-0-muR) where MuR is a segment consisting only of units of inzenoid residues (mononuclear, dinuclear or polynuclear) bonded to the ether oxygen through an aromatic carbon. are excluded.

The hydrocarbon segment 2 segment can be derived from a human tetraxyl-containing material containing a hydrocarbon segment. The size of this hydrocarbon group ranges from a low molecular weight alkyl group to a substantially larger molecular weight polymeric hydrocarbon group.
l can vary widely. When 2 is a low molecular weight hydrocarbon, the acid halide functionalities of Formulas 1(a) and 1(b) can be used to attach the -IsK linkage as described below. The resulting linkages will lead to the introduction of low molecular weight hydrocarbons as additional blocks into the resulting nylon/block polymer. low molecular weight hydrocarbon (CZ)
Examples of segments include 02-07 alkylene.

The preferred two segments in this jI- are polymer hydrocarbon bulk segments. Here, "polymer hydrocarbon segment"
means a carbide compound having a molecular weight of at least about 100 and containing two or more repeating units. Examples of tetraxyl-containing substances that can be used to provide two segments that are polymeric hydrocarbon bulk segments include alkylene (01$P and higher) and polybutadiene diol, polybutadienetriol, polybutadiene Diols and larger polyols of polybutadiene are mentioned. Preferably, the segments that are high molecular weight hydrocarbons have a molecular weight of at least 5000, but K from about t000 to about 25.0
A molecular weight of 0.00 is preferred. For diol conductors, K is a molecular weight of about 1,000 to about 4,000, for triol derivatives, a molecular weight of about 4,000 to about 12,000, and for tetol derivatives, K is a molecular weight of about 4,000 to about 1,000. is the most preferable.

The two segments may also be polysiloxane segments as defined above. Such L segments can be derived from human mixyl-containing compounds with polysiloxane segments. Examples of hydroxyl-containing compounds of this type include, for example, polydimethylsitequinane containing two or more droxyl blind groups.

There are generally at least 500 borosilicate xane segments,
More preferably, such ILs have a molecular weight of about 1,000 to about 2
5,000.

What is the scale containing a combination of each segment of polyester, polyether, hydrocarbon, and polysiloxane in which the two segments in the above formula are completely arranged? Ik1m will be understood. As mentioned above, preferred polyester segments contain polyether segments or polyhydrocarbons. Further, as mentioned above, the polysiloxane segment as defined herein typically contains groups other than cysugaquinane units. It will be appreciated that other combinations of polyester, polyether, hydrocarbon, and polyester segments are possible and are equally useful as the second term filler in the present invention.

In the above formula 1 (aJ and I (b), X is
chlorine or bromine are preferred and salt 1 is preferred. The integer in formula I (and !(b) is at least 2, preferably 2-20, most preferably 2 to about 4; A polyvalent hydrocarbon group (a valence group similar to a+1, which is compatible with the R group in the modified halide starting material in the above reaction formula) (R1 in bJK is an alkyl group, an aryl group, an aralkyl group) group, alkyloxy group, aryloxy group or aruoxy group.

Preferred acid salts of the present teachings are substances of the formula: where X is salt IIA or bromine, b is from 2 to about 4, and R and 2 have the above definitions. . A further preferred embodiment for the inclusion of the jun^ride functionality, as described above, is in which the R group has at least 5 consecutively bonded element atoms to any two RK-bonded carbonyl atoms. This is what we provide. Examples of such R groups include groups derived from adiboyl halide, iso-7ta-yl halide, and tele-7yl halide.

2nd officer* to Shun who was taught here! The acid halide functional materials of the present invention are reacted with lactam monomers to form acyl difunctional compounds which have been found to be useful in the production of polymeric ivy structures. The polymer can be further reacted with a lactam monomer to produce a polymer. If you look at it, the above formula! The acid halide functionality described in (a) is about 4
~12 carbon atoms containing tscutam monomers) and Jl, b, R and 2 are of formula 1 (a
) with the above definition for K] can be produced.

The same INK% formula 1(t))K described above is reacted with a lactam monomer to form the following acyllactam functional substance ul 10 (which is Riff v). , and b%RITh and 2 are the formula ■
(B) having the above definition, and R1 can also be q] can be produced.

The reaction of the second halide functional compound with the acyltcutam monomer to produce the acyltcutam functional material of formula (b) and formula (b) typically involves, for example, cyclohexynane,
This reaction is also carried out in the presence of toluene, acetone or an excess of Tuctam monomer as a solvent and an acid scavenger to facilitate the removal of the hydrogen nitride produced during the reaction. It can be carried out even without the presence of a knowledgeable person. Human Kyoxyl association substance and acid halide agent 111! *The discussion above regarding the use of solvents and reaction conditions for the reaction with Chix applies here as well. Alternatively, the acyltscutam functional material can be synthesized without isolating the intermediate acid^ride functional material (Formula 1(a) or Formula 1(b)) that is produced. 0 formula 1 (aJ case or formula 1 (1
A quantitative reaction in which essentially every halogen in the acid halide of No. 1 is replaced by a lactam group is preferred.

Next, the ceremonial seal (Q and the two seals)
! The acyl lactam monomer can be further reacted with another acyl lactam monomer to produce a acyl lactam monomer.Additional acyl lactam-containing materials can be included in the reaction mixture, but the acyl lactam group should be present in excess of hydroxyl groups in the mixture. This hydroxyl-containing material becomes Kl1 in the nylon polymer. These substances should be mixed in the pot. This reaction mixture II! JK generally includes antioxidants. This reaction is generally a popular base catalyst for the anionic polymerization of lactams. Shi< is Kabu four Kutam! It is carried out in the presence of Danesium pumide or Kabushikta, Mumagnesium chloride. Small amounts of catalyst, for example up to 1 mole of lactam monomers to be polymerized, are useful, but larger amounts, for example 1 mole based on 2 lactam monomers, are useful.
Amounts of -20 mol% or more may also be used. The lactam monomers generally contain 4 to about 12, preferably 6 to about 1
Contains 2 carbon atoms. Particularly preferred is caprolactam (herein meant -butyraclactam); for Q in formulas (a) 11- and stratification (b) the corresponding residues of such preferred lactam monomers are preferable. Relatively short reaction times, such as less than 10 minutes or even less than 50 seconds, and e.g. from about 70°C to about 250°C
, good'! or about 120 DEG C. to about 170 Ctr). Bicutams can be polymerized at acyllactam sites and can also be inserted at ester and and sites.

In this way, Heclrick and Gabb, supra.
The nylon plutopolymer disclosed in US 1ii1 patent Ij1 specification by Messrs. @rt can be produced. The rapid reaction times for producing Tironplotter polymers make the disclosed materials particularly useful in reaction injection molding, as well as other similar applications, such as in-movement of substrates.
ld) coatings, rotational molding, resin transfer molding and pultrusion Iv are also expected.

The relative amounts of lactam monomer and acyl lactam functional polymer used in the preparation of nylon protuta polymers by the above process can vary over a wide range depending on the desired nylon protuta polymer.

The lactam monomer and the acyl lactam functional polymer may be present in a proportion of 99 parts by weight of either one and 1 part by weight St of the other. Preferred amounts are from about 60 to about 90 wt.
of lactam monomer and from about 10 to about 40 weight percent of acyl lactam functional polymer. However, from about 40 to about 70 weight by weight of the acyllactam-functional polymer can be used to prepare the elastomeric polymer. Under typical reaction conditions, the polymerization is essentially quantitative. It is.

That is, essentially all of the tscutam and acyllactam functional polymers are incorporated into the napkin ivy polymer.

In the production of nylon plastic polymers, it is desirable to carry out the polymerization reaction using KjIP in the presence of one or more other substances commonly present in nylon plastic polymers. These include, for example, fillers, plasticizers, flame retardants, stabilizers, fibrous reinforcing agents such as asbestos and gout fibers, dyes and IR family. Such materials have the formula S (a) as taught herein, the formula! (b)
Or it can be introduced into the material of 弐厘 (51) and stratification (cutting) or other substances.

The present invention will be explained in more detail by MK below. These examples are merely illustrative and should not be construed as limiting the scope of the invention, which includes a variety of other variations. 4? All parts, -1 ratios, etc. are by weight unless otherwise specified.

Example Preparation of a Ride Functional Substance 40ff: 4a2F ((LO4?) in toluene
equivalent weight] of “Pluracol J ()P-, 5030 (polyoxydipropylene triol, molecular weight approximately 4ooo)*
* was refluxed to azeotropically remove essentially all water. s
9.4511 (a105
fi amount) of crude ajiboil kutuid was added. This solution was heated to RR.

Hydrogen chloride gas was rapidly evolved during reflux. Mixed - is 1
Refluxed for an hour.

This reaction took place at the intermediate position of the polyoxypropylene triol that had been functionalized with air diboyl chloride to form a tri(acid chloride functional) conductor.

B. Preparation of Acyllactam Functional Substances To the reaction product combined with the above reaction mixture was added 169-dried 1lIIIF opulactam. il & coalesce was refluxed. The R flow bot temperature rose to 185°C. Suitable for generating hydrogen chloride! This occurred at a rate of 11. The progress of the reaction was checked by periodically measuring the residual degree. After flowing R for 15 hours at 185C, the acidity is α077ζ/gra A (m@q/gm
)Met.

This Si liquid was cooled and left overnight. Add more toluene 4511j and bring the solution back to 14o6 pot temperature! did. After further refluxing for 2 hours (total reflux time 15 hours), it was titrated with α1N sodium hydroxide to the end point of 7-norphthalein.
It was 2 meq/gm. When refluxed for an additional KLi hour, this acidity did not change.

This reaction occurs when the chlorine atom in the product produced in A above is replaced by a Kabulactam group, resulting in tri(acyllactam) functionality f! ! An IAII conductor was produced.

C. Production of nylon block polymer Another 1'L8I Zorlacol 0F-3030 was added to the reaction product produced in step B above. The toluene was vacuum distilled and the 25α cabtetralactam was removed by distillation. The resulting fII'fIL was cooled to 75°C and added to it with 84M a4% concentration of bromomagnesium capro2.
lactam (in cabtetralactam) was injected under vacuum. The mixture was stirred vigorously for 20 seconds, the vacuum was applied to nitrogen** and the mixture was poured into a Teflon-lined mold at 130°C.

After 2 minutes, the polymer was removed from the disc and cut into specimens for physical testing. The resulting polymer contained approximately 20% poly(oxypropylene) and had the following properties (measured according to the method described in Examples 29-51 below): tensile strength 5960 pg, 41 M
Pa tensile elongation 30g6 Tensile strength 1280 (pi, 224x105
9 J 157,
000 (pa i), 1082-5MPa isot notch has an impact strength of 66 (ft. bond/in.t.
)% 552 J/Tn.

The following polyols and acid halides were used in the preparation of additional acid halide functional polymers, acyl dicutam functional polymers, and nylon block polymers.

Triol (molecular weight approx. 4β00) Zorlacol (P380) Poly(oxybrobylenet P-380 diol (molecular weight approx. 6,760)
) Plulacol (GP) Poly(oxybrobylenet GP5030 Diol (molecular weight approx. 4000) Zollacol P494 (P49
4) Poly(oxypropylene) tetol (molecular weight approx. 4750) Carbowax (CARB) Poly(oxyethylene) tetol (molecular weight approx. 4700) R45M (R45)
Poly(butadiene) diol (molecular weight approximately 2JOO) Polyolmic x (MIX) N1ax11
50150 (Morne mixture Q4-5667 (Q4) of -34 and GP5030) Silicone polycarbinol seal (molecular weight approximately 9,000) Triol (molecular weight approximately 8ρ00) Table B #! Halide name Terephthaloyl chloride TB part Adipoyl chloride Mu DIP Inftairuku CI Phyto l80P
I80P/TIRI warm mixture (50150% by weight)
I80/'I'ERO Medium Sidibenzoyl Coolide
OBC phenylphosphonylchlora (PP)
C'sul7lyl chloride 8C
Phosphorus chloride POC oxalyl tetralide OXX How many examples, 1lII!
Preparation of Palite Functional Somatics 237-96.0 Ii (2 moles of CLO) of N1ax 1
The solution of 1-54 was dried by removing the water azeotrope of 27- during a 30 minute reflux period. This solution was heated to 21°C.
Cooled to 12.18 # (α06 moles)
Taloylchloride ('I'm! RIE) was added with stirring. 20117'tosted in cyclohexane
A solution of triethylamine (α06 moles) was added over 5 minutes. The temperature rose from 21°C to 26°C and a white precipitate formed. The solution was heated to reflux and it was immediately cooled for 10°C. The fIi #& was removed under vacuum at 80° C. to give 102.48 g of yellow silt. There was no carbon absorption of the trihydride and no hydroxyl absorption, indicating the formation of the desired trihydride functional polymer.

Example: 5m*Preparation containing halide functionality 48.0jl (α01 mol) in 77m cyclohexane
The solution containing 11-34 N1 molecules was dried by removing the water azeotrope of 2711# during 50 minutes of reflux. This polyol S* was cooled to 50°C, and this
6.091! (α034) of enclosed terephthaloyl chloride (TIRIc) was added with stirring. 20
D. Schiff's stomach dried triethylamine 304I in hexane (
The α03 morn solution was added over a period of 10 minutes. The temperature is 4
The temperature rose from 7.5°C to 49°C. The resulting creamy slurry was stirred and heated at reflux for 50 minutes to complete the formation of the acid halide functional polymer.

B. Preparation of acyltscutam-blind saccharomycetes The reaction mixture from the above step was cooled to 42°C and added with 4O
Stirring N (α035 mol) solid cabrotam,
I added while doing so. 20-15 in cyclohexane
4JF ((LO35 moles)) of triethylamine was added over 7 minutes. The temperature rose from 42'C to 53C.

Another 601 portion of cyclohexane was added and the mixture was heated to reflux with stirring for 30 minutes. A clear colorless liquid F was obtained by cooling to 11° C. and passing through Celite. The solvent was removed under vacuum at 80° C. for 3 hours to yield a clear yellow silt of 52.26N. The acidity of the acyllactam blinding compound 1 substance produced is α028 m
It was eq/gm.

Example 4. Preparation of Acyllactam Functionality 227d N of 9&0I (a, 024k) in Cyclohexane
A solution of cabp-lactams of 1ax11-54 and 1II (α062 moles) was dried by refluxing for 1 hour, during which time the water azeotrope of 27- was removed. This solution was cooled to 15° C., and 12.18jF (α06 mol) of teletetralide (TKM) was added thereto with stirring. 12.
66N (a125moln triethylamine solution)
Added a minute or so ago. The temperature increased by 30 CK from 15° C. and a white precipitate formed. The mixture was heated to R flow at 11a, maintained at that temperature for 1 hour, and continued to open to reflux for an additional hour. After cooling the mixture to 10℃, "Ryu Light"
The solvent was removed under vacuum at 080° C. for 3 hours to obtain an amber syrup of 95951.

The fR property of the produced acyl lactam functional polymeric material is a032 m@q/gm "t'".

Example 5 匈28 Substantially the above-mentioned Example 3 except for the specified contents and their usage amounts
(M and B) or further example 5 according to example 4
-28 were carried out. Type and amount of material and method of preparation for each of Examples 5-28 (Hz, 5 or Hz,
4) is shown at $11 IC' for 6 examples 5 Kt, so in some of the examples performed, the reflux of step B was 30
It lasted more than a minute, and in some cases even extended to three hours. Furthermore, in some of the examples carried out according to Example 5, a small amount of methanol or a small amount of anhydrous sodium carbonate was added after 30-60 minutes of reflux in step B to adjust the acidity of the final product. In some of the examples carried out according to Example 4, an equal amount of sodium carbonate was used in place of the methanol added during the reflux step. The acidity of the resulting acyllactam functional material was approximately α028-α3 m@q/gm for each of these examples.

Example 29-51 Production of Nylon Block Polymer
Either O2 or reaction injection molding polymerization (RIM)
was prepared from the acylatatum blinding polymer prepared in Example 5-28.

These methods are described below.

Mu, Nainpu Yotsuta heavy body hand in hand (
IF12? -47) In a mower equipped with a stirrer, a thermocouple and a nitrogen inlet, the acyllactam and the acyllactam agent prepared according to one of the above *5-28 *I! The amounts of A-type prepolymers loaded with prepolymers that are IIE polymers and the quantities used in each of Examples 29-47 are shown in the table. Each platform, tsy's "7 rektor [phase]
(Monnanto Co., Ltd.'s oblique crystal, anti-strengthening agent, polymerization 1.2-di and draw 2.2.4-); linome, dichloroquinoline) was added to the preparation. The mixture was heated under vacuum to distill off the 25-caprolactam and cooled to 75°C. .

A catalyst solution, WItIL of bromomagnedi-9mukazo-tetracutam in caprolactam, was prepared separately.

This catalyst solution [is generally 3 in diethyl ether].
It was prepared by adding a solution of molar ethylmagnezi fp membrane bromide to dry caprolactam and then thoroughly degassing under vacuum. Catalyst solutions of various molar concentrations were prepared. For example, a .alpha.5 molar bromomagnesium caprolactam catalyst solution was prepared by adding 5 moles of 17-11 degree ethylmagnesium tetramite in ethyl ether to 100 g of dry caprolactam and then degassing as described above. The moles of the catalyst solution used for the helium example! I! is shown in Table DK.

Note that Example 35 contained 4 of 711 P117B'/1 m' crushed glass fibers, resulting in a 25 inch (by weight) glass-reinforced nylon vine polymer.

A specific amount of catalyst solution was injected into the prepolymer solution prepared above under vacuum. The specific amounts of catalyst solution used for Examples 29-47 are shown in Table DK. After stirring vigorously for 50 seconds, the vacuum was turned to nitrogen and the contacted mixture was poured into a Teflon-lined potato heated to 130°C.
The solid nylon block polymer that formed was removed after 5-15 minutes of soaking in the 100 ml solution. Polymerization of the prepolymer with caprolactam was essentially quantitative in the production of nylon block polymers.

D HC example 29 5 442 148 a5 355
0 6 517 175 a5 5031
7 74 101 a5 503283
α4114 α526 33? 5A1 176 α53634
10 44J 1,58 α53835
10 44.4 158 a5 3856
11 748 229 House 4057
12 5905 148 House 56°58
1s 9465 240 House 8539
14 7 & 7 300 House 4540 1
5 55B175 a5 3241 16
60 196 α53042 21 62
178 Li 5545 22 55
1S5 a5 5544 25 61 j
34 a5 8045245 169
α65046 25 57 148 (L6
7047 26 5? 149 α6
67B, reaction injection molding of nylon block polymers (Example 4
8-51) Caprolactam and Preparation Example 5-2 in a 500-volume flask equipped with a stirrer, thermocouple, and nitrogen inlet. A prepolymer, an acyl lactam functional polymer thus prepared, was charged.

The amounts of materials used in the preparation of the variant prepolymers and prepolymer solutions in each of Examples 48-51 are shown in Table I
K is shown. t51 7 Lectol H was added to each charge. The mixture was dried by heating under vacuum to distill off 25114 caprolactam, then 75
Cooled to ℃.

Separately, a catalytic solution consisting of bumomagnesium caprolactam in caprolactam was prepared by adding 21 EI of a 3 molar solution of ethylmagnesicum bromide in diethyl ether to dry caprolactam, followed by complete degassing under vacuum. It was done. For example α26%
A solution of polymagnesium caprolactam catalyst was prepared by adding 17 molar 2001 of 3 molar ethyl madanesium bromide in ethyl ether to 2001 dry caprolactam.

Catalyst solutions of various molar concentrations were used as shown in Table ICE.

Reaction injection molding was done by pumping the solution into a closed mold heated to 130° C. Zero equal volumes of prepolymer solution and catalyst solution were brought together by a gear pump, with the exception of Example 48. Then, the prepolymer solution and catalyst solution have a volume ratio of 5.4=1 (prepolymer solution/
catalyst solution] were combined by the same means. Mixing of these 1 fK streams prior to injection into the mold was carried out in-line (with a 6 inch by 2 inch stationary evaporator). A solid nylon block polymer was removed. Polymerization of the prepolymer with caprolactam was essentially quantitative in the formation of the nylon block polymer. Samples were cut for testing.

48 17 60 209 Q.
549 18 65 110
cL2650 19 66 109
α2651 20 46 109
α3 (Note) Yojikomido, 25- was removed in the drying process.

The nylon block polymers produced by either hand casting or reaction injection molding in Examples 29-51 were tested for various properties essentially according to the following procedure.

The test results for Examples 29-51 are provided in Table FK. Regarding these nylon block polymers, Mu8TMD1
The tensile elongation (to failure) measured according to 708 is generally greater than 50%, and in some cases 4
'! It was more than 200-. The polymer of Example 35 was reinforced with 254 wt) P117BMX ground glass fibers.

Example 52-117 Example 52-117 has a minimum molecular weight of about 2. Contains any of the polyester segments containing a polyether segment having a minimum molecular weight of about 2.000. A2 ID fact Il!
Figure 2 shows unexpected results exhibited by a nylon cloth copolymer made from a nylon cloth or acetic acid.

Acid halide functionality - quality is produced from polyethers listed in Table GK below! ! 1 was given. These forged hatsido s4! ! JIIR is prepared by adding the desired polyether solution and terephmeroyl in tetrohydride 1272. 1l of loride
It consisted of manufacturing l111[. From each #l solution, do 6 submerits [K enough #! Nukapenger, or triethyl ain, was added. KI for each 11! The specific polyether used (
The molar amounts of PK) and tele-7-t-4yl chloride (TBM) are shown in Table HK.

Different acid halide materials were prepared for each specific polyether. In each case K, an acid halide functional material containing polyether segments and an acid halide functional material containing polyester segments (containing polyether segments) were prepared. These polyester segments are polyether segments and tele7
Produced by combination with taloyl chloride residue. The polyether segment-containing 12 halide functional materials were prepared from a 2:1 molar ratio for the diol derivatives and a 3:10 molar ratio for the triol derivatives.
On the other hand, these materials containing polyester segments were prepared from a molar ratio of 4:5 for triol derivatives and from a molar ratio of 5:2 for triol haze conductors.

These acid halide to polyether molar ratios are expressed in the table below as H/PJ.

A patch of acyllactam-functional material is produced by adding a solution of cabroloctam and triethylamine (11m!Nucavenger) in each $11[K tetrahydro7 run of acid halide functionality. The molar amounts of cabrotam used for each patch are shown in Table H below.

12/-Ride functional substance to S solution
The addition of Fluid II was made about 7 minutes ago. 1wIIL each
The mixture was heated to reflux at 76°C, and then heated at 11°C for about 1 hour. These liquids were then allowed to cool and approximately 100 d of tetrahydro7ran was added to each. Each patch was then passed through and further washed with 7 runs of tetrahydro (7
After about 211 washes at 511 J, the remaining tetrahydro-7 run was removed under vacuum at 80° C. for about 3 hours.

The IR spectrum of Patch 1 did not show any human tetraxyl absorption except for a strong ester carbonyl absorption and a weaker and carbonyl absorption. This confirmed the production of the acylthuctum sensuality.

Plolo All (molecular weight approximately t,
ooo) Boranol 2010 (2010) Poly(oxypropylene) diol (molecular weight approximately 2,000 mm PPG 3025 (PPG5025) Poly(
Oxybu tetrapyrene diol (molecular weight approx. 00) PPG 4025 (PPG 4025) Poly(oxibu tetrapyrene diol (molecular weight approx. 4,000)
) Menol □ (sy5?50) Ethylene oxide end-capped CP2O70 diol (molecular weight approximately 725)
NIAX 11-54 (NIA) Ethylene oxide end-capped poly(oxypropylene triol (molecular weight approx. 41300) Tanol (sys503) Ethylene oxide end-capped poly(oxypropylene triol (molecular weight approx. 7S20)
0) Plulacol (P2S5) Ethylene oxide end-capped P-580 poly(oxypropylene) triol (molecular weight approx. 760) Table H 1Plolo 2:1 (CL468)
(α936n (α973)2
4:5 (0,468) (α624) (0,
527)5 Y2O102:1 (α251) (α5
02) (0,504)4 4:5
(α251) (α555) (α177
)5 PPG30252:1 (0,171) (α5
42) (α354)16 4:3 to, 171)
(0:228) (Q, 124)7 PP()4025
2:1 (0,120) (α240) LQ, 242
)104:3 (α152) (α202) (CL10
6) 11 CP2O705:1 (α450)
(t550) (t360) 12 5:
2 (α450) (t125) (α909)
13 CP1500 3:1 (cL250)
((α750) ((α7575)14
5:2 (CL250n (α625
) (α555) 15 ap 5:1 (α160
) (α480) (α485) 16
5:2 (α150n (α575)) (
α′506n17 NIAX 3:1 ((111)
((155) (0335)18 5:2 (α179
) (α445) (0361)19 5p4505
5 : 1 ((Lo8n (α24)
((α2424)20 5:
2 (α08) (α20) (l11t5
2) 21 P2S53:1 (0,08) ((α24
．． ) ((α2424)22 5:2 (0,08)
(0,20) Lo, 162)23 3:1 (α06
) (α18) (α1818) B, Preparation of Nyremp Ivy Copolymer Nyremp Ivy Copolymer Separates Each Patch of Acyllactam Functional Material in the Presence of Catalyst Turnip Cum Bromide It was produced by reacting with cabbage lactam. The method used to bond these materials together was reaction injection molding. This technique is well known to fitters and it is
Flow of dissolved acyl lactam functional substances and Kl in turnip lactam! The process consists of directly introducing a stream of clarified Kabmyectam magnesium bromide catalyst into a heated mold.

Catalyst S* was prepared in a Kt650jF flask equipped with a stirrer, a thermocouple-controlled heater, and a nitrogen inlet and distillation head for use in each of the nine-to-four copolymer preparation examples except Examples 84 and 87. It was manufactured by preparing the cabrok tom. The caprocutam powder was dried by distilling off the 501 from the flask under vacuum (using an oil pump to obtain less than 1 m vacuum) at a pot temperature of 125-150°C.

The vacuum was applied to a nitrogen atmosphere and the cablok tam was cooled to 70°C. All atmospheric operations were performed under nitrogen.

Once Kabu Kasumi 2 ctam is dried, 3 molar concentration of ethylmagnesium bromide in diethyl ether @l
[120- was added for 10 minutes while maintaining vigorous shaking.

Solution temperature was maintained at 100°C. The generated ethane and ether were removed by degassing under vacuum (<1 m@) at 90°C for 1 hour. The catalyst solution was heated at 90°C.
were maintained and 200-units were removed for use in each sample preparation. The catalyst solution produced was 11225
The concentration was molar.

With the exception of Examples 64 and f187, Prepolymer Solution 1 was prepared by dissolving the prepolymer, which was Achillestutatum blinding soil prepared according to Batches 1-23 above, in Cabloctum. To each sample solution, Ka5F 7-lectol Htlc diluting agent was added. The prepolymer solution was dried by distilling off 25 WJ of caprolactam. These trials 114fI! The liquid was cooled to 85 DEG C. In Example 84, the catalyst fIII liquid was prepared according to the procedure described above except that only the caprolactam of 225j' was dried by distilling off the 25JF. Ethylmagnesium bromide 5 mo J & I concentration #I Suku 19
- was added to the cablok tam according to procedure 1. The catalyst WI liquid was then maintained at 90°C.

Acyllactam functional material for example 84 is turnip vx9
1811I instead of 0 that was not resolved by K1m during Kutum
of the acyllactam functional material was injection molded into the final nylon Plutz copolymer to yield a 30% by weight polyether. The acyllactam-functional material Kt5I, an antioxidant, was added prior to injection molding.

In Example 87 the catalyst was as described in Example 84 except that 16111 J of a 3 molar noble solution of ethylmagnesium bromide was used.
Manufactured in the same manner and in the same manner as.

Again this acyllactam solution is not dissolved in the turnip lactam and the acyllactam functional material 15 of the batch cliff 12
9jl was used.

The prepolymer batch numbers and amounts of prepolymer and cabrotam that were used to prepare the prepolymer solutions for each of Examples 52-117 are shown in Table J.

Table J 52 10 1 45 1
5253 20 1 87
8854 50 1 140
4555 10 2 57
1385620 2 74 101 5750 2 111 64 5810 3 58138 5920 5 75100 6050 5 115 65 6110 4 54141 6220 4 68 107 6550 4 102 75 6410 5 55 140 6520 5 70 105 6630 5 105 70 67 10 6 55 14
26820 6 65110 6930 6 98 77 7010 7 35142 7120 7 67108 7230 7 100 75 7510 8 52143 74 20 8 64 1
1175 50 8 96
7?76 10 9 34
14177 20 9
68 10778 30 9
102 7379 10
10 32 14580 20
10 65 11081
50 10 97 788
2 10 11 60
11583 20 11 121
5484 30 11
181 --85 10
12 53 12286 20
12 106 6987
50 12 159 -
-88 10 13 43
13289 20 13 8
7 8890 50 13
130 4591 10
14 41 13492
20 14 81 94
93 30 14 122
5394 10 15
58 15895 20 15
75 10096 30
15 113 6597
10 16 56 1599
8 20 16 71
10499 30 1<S 10
7 68100 10 17
54 141101 20
17 69 106102 3
0 17 103 721
03 10 18 35
142104 20 18 6
7 108105 30 18
100 75106 10
19 34 141107 2
0 19 67 10810
8 50 19 10j
74109 10 20
33 142110 20 2
0 65 110111 50
20 98 77112
10 21 55 14
2115 20 25 67
108114 30 25
100 75115 10 2
2 52 143115 20
22 65 110H75
0229778 (Note) Feeding amount, 25 mft Removed in drying process.

Examples 52-83.Ni-four-block copolymers in 86 and 88-117 are 2α52ax2α32 scratches×517
1 in a closed lid heated to 140°C to grow the lumen of 5-
Example 84 and Example 8 prepared by pumping the prepolymer solution and catalyst solution at a :1 flow volume ratio.
7 are respectively 152:1 & tL5:1 in similar molds
was prepared by pumping the brepolymer polymer and catalyst solution at a flow-to-volume ratio of . These combined streams were mixed in a 4" x V4" in-line Keetstas static mixer prior to injection into the mold. Then Example 52
~117 were measured for their impactivity and flexibility according to the following test procedures, i.e., self-glide modulus, isocution impact (these have been previously described) and drive dart test procedures. Test operation is V
, A. r spg Ret by Matonis
ec Bul-1sttnJ (November 1974) K
The operation described is 3175 ■ at a temperature of -29 °C.
(11/2 inch) of a specific NBC held against the sample cylinder by a 5 (L8) (2 inch) diameter disc.
(A inch) 11176 to proboscis (consisting of driving a dart at 4400 inches/min) against K. Energy constants are made with a N1 colet 1094 counting oscilloscope [units are Joule (J) 1 or bond x inches].

The results of these tests are shown in the table below from -1 to -4K. These examples are used to emphasize the effect of molecular weight on impact properties of the polyether type (either diol conductor or triol II conductor), thus reducing the weight of the polyether in the N4B4C copolymer. The arrangement is sorted by and by m ratio.

In the table -1 Self modulus Izotsu impact value Drive dart 52 2268 (529) 21 (Jl
l4) α5 (2,6)58 j517
(220) 64 (12) 2.1
(18,7)64 1972 (286)
69 (C3) (19 (79) 70 2
462 C5,57-91 (17)
-----761855(269) 133
(25) N3 (75, S20 Polyether 53106? (155) 16 (Sleep→
α1 (1°1) 59 1172 (170)
155 (2j') 2.7 (
24,6)65 1482 (215) 1
5s (25n 18 (144)7
1 979 (142) 294 (emergency)
:? 6 (25 6) 77 j248 (1
81) 731 (1f) 157 (12!
i, 1) 30% polyether 54 310 (45) 16 (13)
<, 01 ([15) 60 1220
(177) 475 (&?) Z9
(7α8) 66 614 (89) 50
2 (9,4) 8.5 (741)72
455 (66) 584 (7,2)
12.1 (109,0)78 545
(79) 598 (112) 52
3 (47α2 table K-2 -ge modulus isot impact drive dart 82 2165 (314) 14 G, 0.5)
0.1 (12)88 2144
(Jll) 75 (14,) 0
．． 6 (5,5)94 1889 (274
) 80 (15) 2.9 (26
,1) 100 1441 (209) 155
(2,9) 8J (75,7)106 1
717 (24?) 342 (&4,1 1
9.1 (172 fl) 112 1703 (24
7) 352 (6,6) 82 (7
59) 20% polyether 83 331 (48) 5 (aIJ
<, 1 (Q, 1) 89 924 (1
34) 48 (0,9) al
(2,1)95 1331 (193) 774
(14,5) 2 & 8 (2140) 101 10
20 (148) 9m5I L1&O) 59
．． 2 (53t8) 107 1096 (15
9) 838 (15, near) 3Q, 7
(275A an 113m 745 (108)
715 (1 series 55.7 (500,5)1
13B 731 (106)
54.4 (318) 3011 Polyether 84 (poor reactivity) 90 407 (59) 165 (51)
α1 (0,8)96 444 (60)
630 (118) 2α5 (184,1)
102 415 (6 Showa) 667 (125)
223 (200-5) 108 421 (
61) 619 (1t6) 26.7 (2
59,9) 114 393 (57)
582 (10,9) 26.5 (234
2) Table 3 Bending angle Jurassic impact Driving dart 5
5 1848 (268,) 48 (α9
) 23 (2α5)61 2517 (3
65) 48 ((19) ----67
2215 (521) 59 (tl) −
---75779 (113) 32 (α6)
-----791951(285) 64
(12 N C5 (12,0) 20% polyether 56 125t (182) 101 (19)
2A (218) 62 1282 (186)
107 (243) 5.9 (51
1) 68 1400 (203) 160 (
Fifty) 14? (1519)74 1034
(149) 214 (4,0) 9.6
(863) 80 1220 (177) 65
7 (1 time) 29.6 (266,1 n 50%
Polyether 57 752 (109) 128 (Siri 2.1 (18,9) 65 705 (102)
675 (12,6) 25.0 (207
0) 69 1069 (155) 731 (1
Lily 34.5 (510,0)75 455
(6<S) 139 (2A) 62(5
Series 81 421 (61) 452 (
8,1) 36.4 (3272) Table K-4 Bending modulus Izot impact Drive dart 85 2082 (302) 48 (a9
) 2.4 (2,1)91 1641
(23B) 101 (19) 2.7
(24,0)97 1531 (222)
96 (t8) 40 (35,8)1
03 2006 (29ri 96 (18) 51 (2 & 5) 10? 1696 (246
) 246 (4,6) 1α6
(95,6) 115 1607 (233) 128
(2j 40 t555) 20% polyether 86 5t55 (82J 11 (c
12ri, 01 (0,7)92 1103
(160) 256 (4,8) ,05
(4,3)? 8 1227 (178, l
250 (4,3) 1a8 (96,9)
104 1145 <166) 731 (157) 34.2 (3072) 110 1041
(151) 747 (14,0) 5
α1 <449.9) 116 1207 (1
75) 747 (14,0) 29.5
(2654) 30-polyether 87 283 (41) 21 (a4
) <, 01 (α4)95 452 t6
55) 470 (8B) 0.6 (
5J:J)99 556 (80,6) 785
(14,7)19.1 L17t5)105
607 (8B) 689 (12,9J
25.6 (212,4)111 503 (
73,) 662 (1 series 317 (285
,0)117 448 (65) 525
(9,8) 28.2 (25&5) -1- in the table
K-4K pointed out that their impact tests, izo impact and drive mate tests of nylon block copolymers containing polyether segments or polyester segments containing polyether segments show that the polyether segments are about 2 ,000 shows unexpected results. For example, each t
See Examples 52-57 and Examples 82-87, which contained polyether segments having molecular weights of ooo and 725. They exhibited significantly lower impact properties than the remaining examples, which generally had molecular weights of about 2,000 or greater. Example 8? -90 and Examples 91-95 showed better impact properties, but these had a preferred minimum molecular weight of about 2.
The polyether segments were made from triol-derived polyether segments having a minimum molecular weight of about 1,600 within 1,000. This effect is more pronounced at polyether contents of 10 wt- or higher in the nylon block copolymer, but it is probably because such small amounts of polyether that are precipitated into the nylon block copolymer result in more polyamide segments than polyether segments. This is because the impact is huge.

Furthermore, as noted in Table Show the results outside. Examples 94-96 and 97-99 for triol conductors
And see Examples 64-66 and Examples 67-69 for diol collar conductors, both the triol and diol used had a molecular weight of about 5 Iooo.

Also, as mentioned above, a minimal amount of cross-linking in the composition provides better properties. This is PPG 4025
(Example 70-7)
2 and Examples 75-75) using tanol (Tha
nol ) 8F 3950 (Example 7
6-78 and Example 7? You can understand this by comparing it with that of -81). Tanol 1iiF 5950 was a composition with a functionality of about 21, thus allowing some minimal cross-linking.

Examples 118 to 122 Examples 118 to 122 are the R groups as described above [formula! KJI was prepared to demonstrate the effect of specific R groups on the impact and other properties of nylon block copolymers prepared from prepoly!

As mentioned above, preferred R1 is a hydrocarbon group having a hydrocarbon 11fi and an ether linkage providing at least three consecutively bonded elemental atoms between the two carbonyl groups bonded to R.

Acyllactam functional material is polyether (NIAX)
was produced by reacting with various acid halides listed in Table LK below. Some of the acid halides used (
i.e., 0-7 tal-sunri tetralide and 7-mal acid talolide) produced R groups providing up to 5 consecutively bonded atoms between the two Q carboxyl radicals. The remaining halides forming the R group were others providing two carbonyl groups f14KII or more consecutively bonded atoms. The resulting acid^ride functional materials were then reacted with cabtetralactams (the specific preparation of these materials is similar to the method described above) to produce acyllactam functional materials.These acyllactam functional materials The material was blended in Kabzono lactam and reacted with a catalyst-power lactam solution (prepared according to a method similar to that described above) to form a nylon block copolymer having a 20 wt.-polyether content. These produced nylon block copolymers were subjected to a driving dart test (
Itl) and acetone extractables test (weight loss after 24 hours in Soxhlet extractor 96) Table 0 with K
L 118 m-7 Talic acid chloride 5525 (5147
) 164115F p-7 talic acid tetralide 1 rod 70 (14t1) 1.75120
o-7 talic acid tetralide (L200 (18)
3.38121 Cepacic acid pride 5
5Q8 (3152) 1711227 Malic acid chloride α122 (tli) Impact resistance of 1-N4 block copolymer as seen from the 340 surface (
Examples 118, 11? and 121 are improved when the R group is this RaK-bonded two carbonyl groups Me1' (both provide three consecutively bonded atoms). Please refer.

Although the preferred embodiments of the present invention have been described above, various changes or replacements can be made to the present invention without departing from the scope of the present invention. It is to be understood, therefore, that the invention has been described by way of illustration and not limitation.

Claims (1)

[Scope of Claims] 1) 2 lactam monomer, a basic lactam polymerization catalyst and the formula [wherein, Q rL"N-C-0 (Coco"C" Y tX
C5-C11 fullkylene], a is 1,2
69 is an integer of 3 or 3, b is an integer of 2 or more, R is a 2II group or a polyvalent group selected from a hydrocarbon group and an ether bond-containing hydrocarbon group, and (2) a polyether having a low molecular weight of about 2.000. IIm of a N4-impretuta copolymer, characterized in that it is reacted with an acyllactam-functional substance selected from the group consisting of polyester segments containing polyether segments with ODD. 2) Tsukumem monomer, basic latatum polymerization catalyst and formula) [In the formula, Q is -N-C 0 (where Y is 05 to C11 alkylene, & is an integer of 1.2 or 3) can be,
b is an integer of 2 or more, and R is 2iI selected from an aspect ratio hydrogen group and an ether bonded hydrocarbon group.
i or a polyvalent group, and 2 is (1) a polyether derived from a triol or (2) a segment of a polyester containing a polyether segment derived from a triol]. A process for producing a nylon block copolymer, comprising reacting an acyl lactam functional material. 5) The method of claim 2, wherein Z is (1) a polyether having a minimum molecular weight of 000 or (2) a polyester segment containing a polyether segment having a minimum molecular weight of about 2,000. Method. 4) A lactam monomer, a basic tuctam polymerization catalyst, and a lactam polymer, a is an integer of 1.2 or 3, b is an integer of 2 or more, and R is a dilit or polyvalent group selected from a hydrocarbon group and an ether bond-containing hydrocarbon group, and sZ is a polyether derived from (1) tetoxyl or (2) tetoxyl a polyester segment containing a polyether segment containing an acyl dicutam functional material. 5) A polyether in which z is derived from (1) tetrol having a minimum molecular weight of 4,000! or (2) a segment of a polyester containing a polyether segment derived from tetohyl having a low molecular weight of about 4000. 6) Claims 1 and 2 in which the statement n is ! Taha! 41
The method described in any one of JIt. 7) A method according to claim 6J, wherein the group R provides 5 consecutively bonded elemental atoms between any two RK-bonded carbonyl groups. 8) Said claims wherein the group R provides from about 4 to about 8 sequentially bonded elemental atoms between any two RK bonded carbonyl groups! 11171 [method described. ? ) R is adipoyl chloride, tele7taroyl chloride, trimezoyl chloride, trimellityl chloride2
id, in7-taloyl chloride, bipmelitoyl chloride, pimeloyl chloride, id, glutaryl chloride, benzophenonato-2-carinoyl chloride,
411 selected from the group consisting of oxydiacetyl chloride and oxydiacetyl chloride! 9. The method of claim 8, which is derived from a halide. 10) R is derived from an acid I-lide selected from the group consisting of adipoyl chloride, terephthaloyl chloride, inphthaloyl chloride, taubasic acid chloride and azelaic acid chloride. the method of. 11) Lactam monomer, basic lactam polymerization catalyst and formula ([wherein, Q is -N-cg=o (here, Y is C!S-0
11 alkylene], and the turtle is 1.2 or 3
is an integer of , b is an integer of 2 or more, and R
is a divalent or polyvalent group selected from a hydrocarbon group and an ether bond-containing hydrocarbon group, and 2 is (1)
A polyether or (
2) Acyllactams selected from polyester segments containing polyether segments having at least about 2,000 molecular sacs, and having an average value of b of 2 or more. aS of N4N block copolymers consisting of reacting a composition of functional substances. 12) The method according to claim 11, wherein the formula is: 13) A method according to claim 12, wherein the group R provides at least 45 consecutively bonded elemental atoms between any two carbonyl groups in which the group R is complexed. 14) The method of claim 15, wherein the group R provides from about 4 to about 8 sequentially bonded elemental atoms between any two carbonyl groups in which RK is complexed. . 15) R is derived from a halide selected from the group consisting of adiboyl chloride, terephthaloyl chloride, in7t-tetrayl chloride, sebacyl chloride, and azelayl chloride, The method according to scope item 14. 16) Any of the preceding claims 11 or 12, wherein z is a segment of (1) a polyether derived from a triol or (2) a polyester containing a polyether segment derived from a triol. The method described in one. 1υ2 is a segment of a polyester containing (1) a polyether segment derived from a triol having a minimum molecular weight of about 4000; (2) a polyether segment derived from a triol having a minimum molecular weight of about 4000; 17. The method of claim 16. 18) Polyether derived from (1) tetrol or t! (2) The claimed invention is a polyester segment containing a polyether segment derived from tetohyl! 1. The method according to any one of paragraphs 11 or 12, wherein z is (1) a polyether derived from tetrol having a minimum molecular weight of about 4,000 or (2) a polyether having a minimum molecular weight of about 4,000. 19. The method of claim 1111IIi18, wherein the polyester segment contains a polyether segment derived from ter)al. 20) Claim I in which the polyether segment consists of poly(oxyethylene], poly(oxyethylene), poly(oxybutetrapyrene), or a block polymer of poly(oxypropylene) and poly(oxyethylene)
! The method according to any one of paragraphs 6 or 12. 21) Claim H@Claim 6, where b is 2-4, @
The method according to any one of paragraphs 12 and 20. 22) The method according to any one of claims 6, 12, or 20, wherein Q is the residue of a cabtetralactam. 23) lactam monomer, basic lactam polymerization catalyst and formula % lekylene), a is an integer of 1.2 or 5, b is an integer of 2 or more, and R is a carbonized A divalent or polyvalent group selected from a hydrogen group and an ether-bonded fully blinded hydrogen group, in which the acid group R has at least 43 consecutive groups between any two carbonyl groups bonded to the RK complex. It provides a bonded elemental atom, and 2
is a segment of (1) a hydrocarbon or (2) a polysiloxane, and the average value of b of the composition is 2 or more. A method for producing a four-block copolymer, comprising reacting a composition of 24) The solution according to claim 24, in which the formula is 25. The method of claim 24, wherein the method is derived from an acid halide selected from the group consisting of chlorides. 26) The method according to any one of the preceding claims 6, wi12 or 24, carried out at a temperature of about 70C-, about 250C. 27) The method of claim 26 carried out at a temperature of about 120<0>C to about 170<0>C. 28) A process according to any one of claims 26-1 or 27, wherein the catalyst is cabrolatatum magnezium 9-promide or cabrolatatum madanesium trichloride. 29) A lactam monomer, a basic Tsukume pentapolymerization catalyst and a) formula % formula % now), and a) engineering 1.2'! ! is an integer of 3, b is an integer of 2 or more, R is a divalent or polyvalent group selected from a hydrocarbon group and an ether bond-containing hydrocarbon group, 2 is a segment of (1) a polyester, (2) a polyether, (3) a hydrocarbon, or (4) a polysiloxane. wherein the basic lactam polymerization catalyst is effective to essentially complete the polymerization of the lactam monomer and the acyl lactam functional material within 10 minutes to form the tertiary block polymer. 1. A method for producing a nylon polymer, characterized in that it is provided in a quantity of nylon. 30)) and a polymer segment derived from a lactam (bJ formula [wherein Q is -N-C!0 (where Y is C15-C11
alkylene], a is an integer of 1.2 or 5, b is an integer of 2 or more, and R is a dihydrocarbon group selected from a hydrocarbon group and an ether-linked blind hydrocarbon group. 2 is a polyvalent group, and 2 is (1) a polyether having a minimum molecular weight of about 2,000 or (2) a polyester containing a polyether segment having a minimum molecular weight of about 2, segment) (a)
and segment (b) has an ester bond or an and bond formed therebetween,
Nylon block polymer.