JPS59133217A - Ionomer with improved low temperature properties - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION This application is a continuation-in-part of currently pending US patent application Ser. No. 453.951, filed December 28, 1982.

The present invention relates to ionomers, and more particularly to ionomers having low levels of chain branching.

With metal ions such as sodium or lead iodine...
Partially neutralized copolymers of ethylene and acrylic and methacrylic acids (ethylene ionomers) are widely known and durable molded resins with good tensile properties and excellent abrasion resistance. . The disadvantage of these is that they become excessively stiff (hardness t, 9) at low temperatures.

U.S. Pat. No. 3,264,272 discloses ethylene'/methacrylic acid/acrylic ester copolymers and ionomers made from these materials. 5
High pressure of 0~3000 atm and 150~300℃
At an elevated temperature of 1%, the polymerization in the presence of a polymerization initiator with a number of free radicals is opened i%.

DE 23 41 462 discloses enalene/acrylate 7' acid copolymers and ionomers and reactor temperatures of 150-300'C! is disclosed. No relationship between reactor temperature and physical properties at low temperatures is disclosed. The resulting polymer is disclosed to have modified oxygen permeability. The examples were carried out at a humidity of 215° C., and it is thought that such materials did not have good low-temperature properties.

In accordance with the present invention, a homopolymer can be copolymerized with ethylene, unsaturated carboxylic acids, and ethylene, and has a low glass transition temperature.
at least one softening comonomer
The ionic copolymer has improved low temperature properties, where the unsaturated carbonic acid is acrylic acid, methacrylic acid.

maleic acid, fumaric acid, itaconic acid, and maleic acid,
selected from the group consisting of fumaric acid and hafester of itaconic acid; The copolymer contains elements of the Periodic Table of the Elements (7) Ia, Ib, IIa, II
having about 3 to about 90% of the carboxylic acid groups ionized by neutralization with metal ions selected from groups b, l1la, rVa, VTb and Branching 2.8
Ionic copolymers are provided that are characterized by low levels of chain branching.

In accordance with the present invention, an improved method for producing ionic copolymers with improved low temperature properties is provided, wherein the method is selected from the group consisting of direct copolymerization and grafted 54 diposition; , (A) the direct copolymerization involves polymerizing ethylene, an unsaturated carbonic acid, and at least one comonomer at elevated temperatures in the presence of free LjlX initiator, followed by the direct copolymerization of the resulting direct copolymer carboxylic acid. and CB) the graft copolymerization consists of neutralizing the groups with metal ions, and CB) the graft copolymerization of ethylene and at least one comonomer in the presence of a free 'X polymerization initiator.
polymerization at elevated temperatures to craft the unsaturated carboxylic acid or anhydride onto the ethylene/comonomer polymer backbone, followed by neutralization of the carboxylic acid groups of the resulting craft copolymer with metal ions; The improvement comprises selecting the comonomer from the group consisting of softened comonomers, characterized in that they can be copolymerized with ethylene to produce homopolymers with a low glass transition temperature, and fZ fKQ hydroxide from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and halfesters of maleic, fumaric and itaconic acids, the copolymer having a molecular weight of from about 10 to about 87 : 4% ethylene, about 3 to about 30% by weight of acid, and about 3 to about 30% by weight of softening comonomer, the polymerization temperature is about 100 to about 200°C, and the carboxylic acid groups of the copolymer are About 3 to about 90% of the elements are Ia, Ib, 11a, IIb, m of the periodic table of one element.
a, [Va, vtb and 2 groups] neutralized with metal ions.

Surprisingly, it has now been found that a class of ionomers derived from ethylene, softening comonomers and methacrylic acid have improved low temperature properties. Produced at low reactor temperatures and has reduced chain branching of ice cubes (
And these polymers containing adequate softening comonomers do not harden as much at low temperatures and harden significantly when compared to ionomers made at high reactor temperatures that contain softening comonomers that do not produce low-gates transition homopolymers. Iono 1- was provided with improved flex crack resistance (loss flex).

They are therefore useful as injection molded items such as ski boots and ice skate shells, and as coatings for structures. - In addition, the ionomers of the present invention have superior low-temperature properties and low hardness compared to commercially available ionomers, so that they can be used in / - rata (balata is L
rans-1,4-polyisoprene). Therefore, it consists of a wick and a cover.

A golf pole whose cover is comprised of the ionic copolymer of the present invention will have a similar impact sound and feel to golf poles made with balata covers. The ionomers of the present invention also include:

7'S can also be used as a modifier for other thermoplastics
, Cocote acts very effectively as a toughener.

The uninvented polymer must be a copolymer of ethylene, an unsaturated carboxylic acid, and at least one softening comonomer that can be copolymerized with ethylene to produce a homopolymer with a low glass transition temperature;
The copolymer is partially neutralized with metal ions.

Unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, and maleic acid,
It can be selected from the group consisting of fumar and itaconic acid hafester. Preferred acids are methacrylic acid and acrylic acid.

The softening comonomer is n-propyl-1n-butyl-2n
-Octyl-12-ethylhexyl-1 and 2-methoxyshethyl acrylates. Preferred alkyl acrylates are n-butyl-12-ethylhexyl-1 and 2-methoxyethyl-acrylate.

Softening comonomers include n-butyl, n-hexyl, 2-
It can also be an alkyl vinyl ether selected from the group consisting of ethyl hexachloro, and 2-methoxy 1 tyl-vinyl ether. Preferred alkyl vinyl ethers are n-butyl vinyl ether and n-8, chizyl vinyl ether.

In the present invention, other softening comonomers which can be copolymerized with ethylene and are characterized in that they produce homopolymers with a low glass transition temperature may also be used in place of the softening comonomers described in 1. It is suitable in addition to this. These things were created by Jay Brandrup (J.B.
randr.

p) and E.HImm
Polymer Handbook 2nd edition (Pol
ymer Handbook, Second
Edition), J. Wiley and
5oz, New York.

1975 “Calanu transition temperature of polymers”
Glass Transition Temper
ture of Polymers) J, the contents of which are attached herein for reference. Such softening comonomers can thus be, for example, acrylates, and vinyl ethers and vinyl esters other than those specifically mentioned in paragraph 1.

The copolymer contains from about 5 to about 15 wt.% ethyl μ/, from about 3 to about 30 wt.% unsaturated carboxylic acid, and from about 10 to about 60 wt. % softening comonomer. Preferably, the copolymer contains about 60% to about 75% ethylene, about 5% to about 15% modified unsaturated carboxylic acid, and about 10% to about 30% softening comonomer.

The copolymers of the present invention contain sodium, potassium, zinc,
Ia, Ib, Ila, IIb, ma, ffa, ■ of the periodic table of one element such as calcium, magnesium, lithium J1, aluminum, nickel, and chromium J,
About 3 to about 90% of the ionized carboxylic acid groups are neutralized with metal ions selected from groups b and
have Preferably, the copolymer is ionized by neutralization with metal ions selected from the group consisting of sodium, potassium, zinc, calcila 1, and magnesium to free the carboxylic acid groups from about 35% to about 75% ion.
It shall be.

The ionic copolymers of the present invention can be directly or grafted.
(Can be produced by polymerization. Direct copolymerization U: ethylene, an unsaturated carboxylic acid and a softening comonomer in the presence of a *# group polymerization initiator at about 100 to about 200 °C, preferably about 140 to about 160 °C or At an elevated temperature of about 130 to about 145°C, at high pressure, e.g.
Pa (20°t) 00 psi) preferably from about 140 mPa (20,000 psi) to about 350 m
(50,000 psi) followed by neutralization of the carboxylic acid groups of the resulting direct copolymer with metal ions. Suitable interest rates are discussed in detail in U.S. Pat. The disclosure content is here, cleavage,
It is attached for this reason.

The graph [-copolymerization method uses ethylene and softened copolymer 2) to free 21; in the presence of a polymerization initiator about 100 to about 2
00°C, preferably from about 140 to about 160'0 and from about 130 to about 145°C, at elevated pressures, such as at least 140 mPa (20,000 psi),
Preferably about 140 mPa (20,000 psi)
~ Approximately 350 mPa (5 o, o a o p
s i), the unsaturated carboxylic acid or anhydride is grafted onto the ethylene/softened comonomer polymer backbone, followed by neutralization of the carboxylic acid of the resulting craft copolymer with metal ions. It can be done by doing.

The ionomer of the present invention includes nylon, vopropylene,
Propylene-ethylene copolymer, linear polyethylene,
and may be blended with other materials such as ethylenic/unsaturated leponic acid copolymers.

These blends generally find use as reinforced thermoplastic materials.

The ionomers of the present invention containing the monomers specified in 1- and obtained at the low reaction temperatures specified in It is characterized by up to about 2.8 chain branches per 1000 @sun.

The following examples are intended to illustrate the invention. , all parts, percentages and proportions are by weight unless otherwise indicated.

Comparative Example J containing n-butyl acrylate, ethylene and methacrylic acid, at a reactor temperature of 220
It was prepared by 1.1 sustained polymerization carried out at °C and 190 mPa (27,000 psi). The addition of Moatsumar was 10, t% of Metagril M (MAA), 17% of n-funal acrylate (nBA) and 72% of ethylene.
．． It was adjusted to form a - with poly containing 9%.

Polymer (basic resin) containing sodium carbonate 11-1
It was converted to the sodium ionomer by reacting with a thickening agent. That is, 1000 g of copolymer was added as a thickener (containing 1196 MAA) and melt flow was 10.
50% Na2COa/H't in ethyl/methacrylic acid copolymer at 0 g/10 min.
It was made to react with 72 g of O (containing O). Anti-1.1′:, ha,
Twin Suff 1,) It was carried out in an extruder of knee piece J using the following conditions: Hitting and deafening J Tomoe's Nucleu speed - One blood crossing N knee Ward knee O - □P, P
M l 2 3 4 550
i7,5 2:E 247 262 280
Speed I boat Chastity C water supply X combined lbs/i>r, '+nAig cc/hr5
30. 20 The polymer of Example 1 was heated to 140'C and l 90mPa.
(27,00 Qpsi). The addition of the comonomer was adjusted so that the composition of the polymer was the same as that of Comparative Example 1.

Extrusion molding of polyester as used in Comparative Example 1~f
1ilfi was converted to an ionomer.

However, in this case, -2.2 Nia Kg in poly-11) thickener (30% Z in E/IOMAA copolymer)
1 (comparison of the results of the polymers of Example 1 and Example 1). [Bigger throat with warmer temperature] 1 song shows an increase in modulus 7 1,,, -
Only poorer flex crack resistance (loss flex) at 20°C
- is indicated. The composition and properties are summarized in Table 1.

For the ethylene/n-butyl methacrylic copolymer of Comparative Example 1 and Example 1, C-13
NMR analysis was also carried out.6 The data obtained showed that the low anti-M
4: By using the chamber temperature (140°C), 2.
The backbone methylene i o
o rjj It was shown that +43 of the alkyl branch around G' was reduced by almost half (the chain branch table below is unknown)
6 Shao Gongxiang, g2jZ Skeletal methylene 10 00 Butyl or MA 11. r, B A Reactor Larger A Example-1 Multi-Ogihai Σ Kawado Kouki and 511 Nichu 9
Example 1 i(1,117,02204,61B
, 5 ], 7.0 140 2.5 h or Example 2 and 3'
Using a composition containing 24% A and 67.4% ethylene, the pressure was 190 mPa (27,000 pSj).
and 195°C. This polymer was subsequently ionomerized with zinc acetate on a two-roll mill. , E! First, polymer loog was added to Zn(OAC)2 in 25 cc of water.
The mixture was reacted with 206.6 g of medium 2H at 200°C. The final ionomer had a melt inden loss of 2.8.

The polymer of Example 3 was prepared in a manner similar to that of Comparative Example 1 and Examples 1 and 2. But 12, reaction is 1
The experiment was carried out at 40° C. in an attempt to match the composition of Example 2. That is, a polymer containing 9.4% MAA, 22.4% nBA, and 68.2% ethylene was prepared and converted into an ionomer.

For conversion to -, add 1 kg of polymer, -1 kg of water,
, Zn(OAc)2 dissolved in 50 c c
*2H? 11 by reacting at 190-200'C in a 6-inch two-roll mill 1 with 60g of
I made it. The resulting ionomer was molded and its physical properties were evaluated.

As a result of evaluation of the ionomer of Example 3, this
It has a lower flexural modulus than that of Example 2, −20
It has been shown to have significantly improved loss bending resistance at °C. The composition and properties are summarized in Table 1.

1 Comparative Examples 2 and 3 These polymers were heated at 140°C and L 90mPa.
(27,000 ps i) and 70% ethylene.
3%, inbutyl acrylate (iBA) 19.8%,
t) containing 9.9% of methacrylic acid was converted into an ionomer. The flexural modulus and loss flexure of these ionomers demonstrate that n-butyl acrylate polymers are superior to isobutyl acrylate polymers. Homopolymers of iBA exhibit relatively high glass transition temperatures. The composition and properties are summarized in Table 1.

Paleo-Shark 1 rows 2 and 3 are also sodium iono 1
- illustrates that there is little or no difference between the leaded ionomer and the leaded ionomer. The improved flex crack resistance and reduced cold hardness are not attributable to the type of ion, but rather to the degree of softening comonobion and chain branching.

6-row nylon containing lead 7-(O/7-3Q%) (Z'ytelR+ 1011.E, 1.d
uFont de Nemours and
C.

mpany) + 7) Blade 7 de to primary composition: E/28,
OnBA/10.1 was prepared by neutralizing a copolymer of MAA. Meltbushi-71・harai/
Three times were produced in a screw-type extruder-L using a high-shear screw design and a melt temperature of 270' (:!). The molded specimens were molded by injection molding to determine their flexural modulus.The results of physical testing of these molded specimens are summarized in the table below.

Tensile strength at break M P a 47 Cpsi')
6800 elongation (work 1%)
110 flexural modulus (MP a 1500Cpsl) in the dry state immediately after
222,000 Notch Ein Soto Impact 3''' At 23℃ J/m 1400ft-1b
/in 27 J/m 460ft at -20°C
-! b, /i in 8, 6111JI9
+ (1) Tensile strength and elongation percentage were determined according to ASTM-638.

(2> lJ1 missing eyelid>・To pull is ASTM-25
6 (Koyomata was measured.

The data is unfinished 1!1li6 low nylon (Zytel/
Compared to Suke 101), the nylon is significantly strengthened and the fi
lii demonstrates the ability of these ionomers to withstand improved toughness.

Special; i'1 application filed - 1 person other than E.I. DuPont de Nimore

Claims (1)

[Claims] (1) Ethylene, an unsaturated carboxylic acid, and a homopolymer that can be copolymerized with ethylene and has a low glass transition temperature. at least 1
an ionic copolymer comprising a species of softening comonomer, the ionic copolymer having improved low temperature properties;
wherein the unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and halfesters of maleic, fumaric, and itaconic acids, and the copolymer contains from about 10 to about 87% by weight. ethylene, about 3% to about 30% modified unsaturated acid and about 10% to about 30% modified
Containing about 60% by weight of the softening comonomer, the copolymer has elements I a, I b, IIa, I of the Periodic Table of the Elements.
from about 3 to about 90% of the carboxylic acid groups ionized by neutralization with metal ions selected from Groups Ib, IIIa, IVa, Ib and I, and the copolymer has a chain content per 1000 backbone methylene units. It is characterized by a low level of chain branching of up to 2.8 branches. ionic copolymer. 2. The ionic copolymer of claim 1, wherein said softening comonomer is selected from the group consisting of alkyl esters of acrylic acid, alkyl vinyl ethers, vinyl varnishes, and vinyl siloxanes. 3. The ionomer of claim 2, wherein the metal ion is selected from the group consisting of sodium, potassium, zinc, calcium, bugnesium, lithium, aluminum, nickel, and chromium. 4. The softening comonomer is selected from the group consisting of alkyl esters and alkyl vinyl ethers of acrylic acid, wherein the alkyl group of the acrylic ester is n-propyl, n-butyl, n-octyl, 2-ethylhexyl, and 2-ethylhexyl. - selected from the group consisting of methoxyethyl,
The furkyl group of the ether is n-butyl, n-hexyl,
Claim 3, qr consisting of selected from the group consisting of 2-ethylhexyl and 2-methoxyethyl
The eye ionomer described in 65 is a direct copolymer, the unsaturated acid is selected from the group consisting of acrylic acid and methacrylic acid, and the softening comonomer is selected from the group consisting of alkyl esters and alkyl vinyl ethers of acrylic acid. , the alkyl ester is selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate, and the alkyl vinyl ether is selected from the group consisting of n-butyl vinyl ether and n-hex/ruvinyl ether. The ionomer according to claim 4, comprising: 6. the ethyl alcohol is present in an amount of about 60 to about 75% by weight, and the unsaturated acid is present in an amount of about 5 to about 15% by weight;
The alkyl ester is present at about 15% to about 25% by weight, and the alkyl vinyl ether is present at about 3% to about 3% by weight.
Ionomer according to claim 5, wherein the ionomer is present in an amount of i%. 7. The copolymer comprises about 35-75% of the carboxylic acid groups ionized by neutralization with metal ions selected from the group consisting of sodium, potassium, zinc, calcium and magnesium. The ionomer according to claim 6. 8. The ionomer according to claim 1, wherein the ionomer is a graft copolymer. 9. An improved method for producing ionic copolymers with improved low temperature properties, wherein the method is selected from the group consisting of direct copolymerization and graft copolymerization, wherein: (A) the direct copolymerization The polymerization involves polymerizing ethylene, an unsaturated carboxylic acid, and at least one comonomer at elevated temperatures in the presence of a liberating initiator, followed by neutralization of the carbonic acid groups of the resulting direct copolymer with metal ions. and (B) the graph b, t+'' polymerization consists of polymerizing ethylene and at least one comonomer at elevated temperatures in the presence of a !# group polymerization initiator to form an unsaturated carboxylic acid. The improvement consists of L-hegelaffting of the ethylene/comonomer polymer backbone with an acid or anhydride and subsequent neutralization of the carboxylic acid groups of the resulting graft copolymer with metal ions, said comonomer being copolymerized with ethylene. and the unsaturated acid is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and maleic acid, the copolymer comprises about 10 to about 87'% ethylene, about 3 to about 30% by weight
of acid and from about 10 to about 60% by weight of a softening comonomer, the polymerization temperature is from about 100 to about 20,000, and from about 3 to about 90% of the carboxylic acid groups of the copolymer are found on the Periodic Table of the Elements. Ia, Ib, IIa, IIb, ma, IV
An improved method comprising neutralization with metal ions selected from groups a, b and group . 10. Process h according to claim vIJ, paragraph 9, wherein the softening comonomer is selected from the group consisting of alkyl esters of acrylic acid, alkyl vinyl ethers, vinyl esters and vinyl siloxanes. 11. The metal ion is sodium, potassium, zinc, calcium, magnesium, lithium, aluminum,
ji#: according to claim 10 sn selected from the group consisting of nickel, and chromium. 12. The softening comonomer is selected from the group consisting of alkyl esters and alkyl vinyl ethers of acrylic acid, wherein the alkyl group of the acrylic ester is n-
Propyl, n-butyl, n-octyl, 2-ethyl l-
and 2-methoxyethyl, and the alkyl group of the ether is selected from the group consisting of n-butyl, n-hexyl, 2-ethyl, and 2-methoxyethyl. Claim 1
The method described in Section 1. 13. The process is direct copolymerization, the unsaturated acid is selected from the group consisting of acrylic acid and methacrylic acid, the softening comonomer is selected from the group consisting of alkyl esters and alkyl vinyl ethers of acrylic acid, and the alkyl ester is selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate, and the alkyl vinyl ether is n-
- butyl vinyl ether and n-hexyl vinyl ether. 14. The polymerization temperature is about 140 to about 160°C and the polymerization pressure is about 140mPa (20,000psi) to about 350℃.
14. The improved method of claim 13 comprising: +nPa (50,000 psi). 15. The polymerization temperature is about 130 to about 145 °C and the polymerization pressure is about 140 mPa (20,000 psi) to about 350 °C.
14. The +3 improved method of claim 13, wherein mP & (50, QOOps i). 16, the ethylene is present in an amount of about 65 to about 80% by weight, and the unsaturated acid is present in an amount of about 5 to about 15% by weight;
The alkyl ester is present in an amount of about 10 to about 25% by weight, and the alkyl vinyl ether is present in an amount of about 10 to about 3% by weight.
The improved aspect of claim 13, wherein the J-length is present in an amount of 0% by weight. 17. The copolymer contains sodium and potassium.11. The improved method of claim 14 comprising having about 35-75% of the carboxylic acid groups ionized by neutralization with metal ions selected from the group consisting of zinc, calcium and magnesium. Method. 18. The improved method according to claim 9, wherein the square size is graft copolymerized. 19. The improved ionomer of claim 1 and 5-iron, polypropylene, propylene-ethylene copolymer, linear polyethylene, and ethylene,
Thermoplastic blend with a material selected from the group consisting of /unsaturated carboxylic acid copolymers. 2. A thermoplastic blend of the improved ionomer of claim 6 with a material selected from the group consisting of nylon, polypropylene, propylene-ethylene copolymers, linear polyethylene, and ethylene/unsaturated carboxylic acid copolymers. 2. A thermoplastic blend of the improved ionomer of claim 7 with a material selected from the group consisting of nylon, polypropylene, propylene-ethylene copolymers, mv polyethylene, and ethylene/unsaturated carboxylic acid copolymers. 22, a core and a cover, the cover comprising an ionic copolymer according to claim 1. golf pole. 23, comprising a core and a cover, the cover comprising an ionic copolymer according to claim 3. golf pole. 24. A golf hole comprising a core and a cover, the cover comprising the ionic copolymer of claim 5. 25. A golf ball comprising a core and a cover, the cover comprising the ionic copolymer of claim 7. 26, a core and a cover, the cover comprising an ionic copolymer according to claim 8. golf pole.