DE3313442A1 - POLYMER COMPOSITION - Google Patents

Description

In particular, the present invention relates to a new polymer composition having superior properties, the is composed of a modified polyester resin in which the di- (monohydroxyphenyl) -substituted, aliphatic Hydrocarbon polycarbonate polymer and part of the tetramethylene glycol forming the polytetramethylene terephthalate by a glycol with an alkyl group or alkyl groups was replaced in the 2-position by 1,3-propanediol.

The polytetramethylene terephthalate resin (hereinafter referred to as

PBT resin) is a highly crystalline thermoplastic polyester resin and has excellent properties Affinity for various fillers and additives Due to this property, reinforced PBT resins,

which fiberglass, mica, talc and fire retardants 25

added excellent properties. For example, these resins are widely used in applications including electrical devices, electronic parts and automobile parts. In other words, own PBT resins high mechanical strength, long life

durability, weather resistance, chemical resistance, heat resistance, Dimensional stability and electrical properties. Polytetramethylene terephthalate resins have one higher degree of crystallization, compared to poly-

_o _ ethylene terephthalate resins and have a higher crystal

lization ratio. Therefore, the cooling solidification rate is high and the flowability good, creating a

excellent moldability of the resin results. The PBT resins are thus engineering plastics with a good Balance between the electrical and mechanical properties as well as the processing properties.

However, PBT resins have the following disadvantages:

(1) PBT resins inherently have poor dimensional accuracy, compared to non-crystalline plastics and plastics which are difficult are to be crystallized. This difference becomes particularly clear under the influence of a temperature distribution in a metal mold. PBT resins are also subject to a shape shrinkage ratio, which depends on the thickness of the plastic. If the cooling speed is not constant, the shaped will tend PBT product used to deform and shrink from shape. This property increases the anisotropy of shrinkage the fiber orientation in glass fiber reinforced PBT resins. The molded product tends to Deformation and creates the so-called warpage.

(2) Unreinforced PBT resins lack plasticity and are susceptible to nicking. In order to overcome these drawbacks, various mixed resin compositions have been proposed. A combination of a PBT resin with a basically non-crystalline resin, a polycarbonate resin, is of particular interest. With this combination, the glass transition temperature of the polycarbonate is increased to 15O ⁰ C and increases the impact resistance as well. Based on this finding, there are high expectations of the mixed materials, and mixed compositions having high thermal deformation temperatures and strengths at high temperatures were actually obtained. The improvement in impact resistance by combining the

However, the resin with a polycarbonate was not enough pronounced and none of the mixed materials have the needs as far as impact resistance is concerned the user satisfied.

After extensive investigations with regard to this problem, it has been shown according to the invention that a polymer composition with high thermal deformation temperature and strength at high temperatures with excellent impact resistance and high surface gloss can be obtained by a modified polyester resin is combined with a polycarbonate.

The present invention thus provides a polymer composition, which is composed of a polyester resin (I), the acid component of which consists of terephthalic. acid and its glycol component consists of a mixture of 1 to 25 mol% of a glycol of the

²⁰ given formula (1) and 99 to 75 mol%

Tetramethylene glycol, and a di- (monohydroxyphenyl) -substituted, aliphatic hydrocarbon polycarbonate (II), the proportions of (I) 5 to 95

% By weight and of (II) 95 to 5% by weight, 25

HO-CH ₂ -C-CH ₂ -OH (1)

Kp

where R ₁ and R _{2 are} hydrogen or an alkyl group having 1 to 4 carbon atoms, where R ₁ and R _{2 are} not simultaneously hydrogen.

The modified PBT resin used in the present invention is a polyester resin whose acid component is terephthalic acid and whose glycol component is from 1 to 25

Mol% of a glycol of the formula (1) given above and 99 to 75 mole percent tetramethylene glycol consists.

Typical examples of the glycols given by the formula (1) are 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol. Of these, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol (neopentyl glycol) are for the use according to the invention is particularly suitable.

The modified PBT resin of the present invention can be used in any of using the procedures listed below

will. 15th

Basically the mixed product is made by adding (2) and / or £ 3) to (^) alone or (J ^, where (T) is the resin composition made of PBT resin,

© a resin composition consisting of a polyester polymer, this is obtained by the polymerization reaction of terephthalic acid and 2-methyl-1,3-propanediol and (5) a resin composition consisting of one Polyester copolymer obtained by a polymerization reaction of terephthalic acid and tetramethylene-25

glycol and 2-methyl-1,3-propanediol mean.

The method used for mixing can be a chemical Process in which the starting materials are dissolved in a solvent, or a mechanical process, 30th

in the case of rollers, Banbury mixers, extruders or molding equipment be used in a standard procedure.

_O1 _ For the preparation of the resin compositions (T), (2) and ob ^v - ^v «- ^

(3) The conventional method of making polyesters can be used without further modification. That is, the resin compositions can be prepared

by means of the direct method in which the dicarboxylic acid compound and the diol compound is directly polycondensed, or by means of the transesterification process, in which the polycondensation occurs through a transesterification reaction between a low molecular weight alkyl ester compound a dicarboxylic acid compound with a diol occurs.

The production of a polyester copolymer (3) from terephthalic acid and tetramethylene glycol and 2-methyl-1,3-propanediol is described below by way of example. One mole of dimethyl terephthalate and an excess of one or a 1.1 to 2.0 times total molar excess of a mixed diol of tetramethylene glycol and 2-methyl- ¹ ^ 1,3-propanediol undergo a transesterification reaction in a stream of nitrogen using a standard esterification catalyst under normal pressure and subjected at a temperature of approx. 150 to 24O ⁰ C. The methanol produced is distilled off and the necessary amount of the catalyst, discoloration inhibitor and other additives are added. The reaction mixture is allowed to undergo a polycondensation at about 200 to 280 ° C. under reduced pressure of less than 5 mm Hg. The catalyst employed above can be selected from a wide range of compounds. Examples are titanium compounds, such as tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium and tetrabutoxy titanium, tin compounds such as di-n-butyltin dilau-

rat, di-n-butyltin oxide and dibutyltin diacetate as well 30th

Combinations of the acetic acid salts of magnesium, calcium

or zinc with antimony oxide or the titanium compounds listed first. These catalysts are in the field from 0.002 to 0.8% by weight, based on the total copolymer produced, is used. Discoloration inhibitors, 35

which are phosphorus-containing compounds, such as phosphorous acid, phosphoric acid, trimethyl phosphite _f tridecyl phosphite, triphenyl phosphite, trimethyl phosphate, tridecyl

phosphate and triphenyl phosphate, are effective. It is preferred to use such a discoloration inhibitor in the range of 0.001 to 0.3% by weight based on the total copolymer formed.
5

The poly-2-substituted 1,3-propylene terephthalate component, consisting of terephthalic acid and 2-substituted 1,3-propanediol, as part of the modified according to the invention Polybutylene terephthalate resin (I) is in an amount of 1 to 25 mol%, preferably 1 to 20 mol%, based on the total polymer (I) included. Is the amount of the poly-2-substituted 1,3-propylene terephthalate component less than 1 mol%, the mixture is not improved in plasticity and mold shrinkage. When the amount of this component is more than 25 mol%, in the resulting PβT resin, Melting point and the degree of crystallization are reduced, whereby the thermal and mechanical strength is reduced

will. For this reason, the resin is difficult to mix with the polycarbonate (II) because the resin and the polycarbonate are too different from one another in terms of thermal behavior.

The modified polyester resin (I) used according to the invention is produced using terephthalic acid, 2-substituted 1,3-propanediol and tetramethylene glycol as starting materials. However, it is also possible to use other copolymer components such as tetravalent aliphatic carboxylic acids, such as adipic acid,

on

Azelaic acid and sebacic acid, polyvalent aromatic carboxylic acids such as isophthalic acid, trimellic acid, Pyromellitic acid and 2,6-naphthalenedicarboxylic acid and polyols, such as ethylene glycol, propylene glycol, 1,6-hexanediol, 1,4-dichlorohexanediol, cyclohexanedimethanol, trimethylolpropane and 'pentaerythritol, each in suitable amounts depending on the desired goals.

The polycarbonate resin (II) used in the present invention is a polycarbonate of di- (monohydroxyphenyl) -substituted aliphatic hydrocarbons. In particular, it is a bisphenol polycarbonate, whereby 4,4'-dihydroxy Diphenylalkane polycarbonate is particularly preferred. The most preferred example is the polycarbonate of bisphenol A (4,4'-dihydroxy-2,2'-diphenylpropane).

It is desirable that the polycarbonate (II) have a molecular weight of about 30,000 or over 30,000.

It is possible in the polymer composition according to the invention to incorporate suitable amounts of additives known per se, depending on those in the composition

! 5 desirable properties and effects. For example lubricants such as an organic acid amide, wax, crystallization nuclei, oxidation inhibitors, Ultraviolet rays absorbing agents, static electricity inhibitors and fire retardants,

20 can be added.

The polymer composition according to the invention can also about 5 to 40 wt .-%, preferably 10 to 30 wt .-%, organic or inorganic fibers or particles as contain reinforcing fillers. Of the fillers, glass fibers are particularly preferred, the total weight being of this filler should be in the range specified above. It was known to improve mechani properties of the resins and in particular for

increasing the impact resistance of polyesters, such as

PBT resins to use glass fibers. The addition of fiberglass to a composition according to the invention shows even a greater effect than predictable and the

Impact resistance is increased far more than expected.

The amount of the composition according to the invention added Glass fibers can thus be smaller than normal, but still achieve the desired effect

* ■ will.

The composition according to the invention contains 5 to 95% by weight, preferably 20 to 80% by weight, of the polycarbonate and 95 to 5% by weight, preferably 80 to 20% by weight, of the modified PBT resin. Is the amount of used Polycarbonate less than 5 wt%, the impact resistance of the blended composition will not improved. If this amount exceeds 95% by weight, then adversely affects the melt flow property of the resin. In the preparation of the polymer composition according to the invention, both components can contribute a temperature above the melting point of each polymer, the preferred temperature range

is 150 to 300 ^0C . The mixing process can be a chemical process in which the components are dissolved and mixed in a solvent, or a mechanical process using rollers, Bunbury mixers, extruders, or molding machines. In each

In this case, the normally used procedure or

the equipment is used.

Although the reason that the present invention is a resin composition with outstanding impact resistance

is not fully clarified, the following may be the case

Theory.

The PBT resins generally have a low impact resistance, since they are resins with high crystallinity. 30th

On the other hand, the polycarbonate resins are generally excellent in impact resistance because they Are polymers with a low degree of crystallinity. A simple blend of a PBT resin and a polycarbonate

natural resin does not, however, improve the impact 35

strength to the expected extent. This disappointing result was attributed to the fact that the

Liability parameters for the PBT resin are 10.8 and for the polycarbonate resin 9.8. The difference in solubility parameters of 1.0 and the fact that the PBT resin is a highly crystalline polymer and the polycarbonate resin is a relatively non-crystalline polymer were considered to be the cause of poor mutual solubility. That is, the mixed resin consisting of a PBT resin and a polycarbonate resin contains a PBT phase, an area in which both resins are mutually dissolved and a polycarbonate phase. These phases exist relatively independently of each other, so this is the cause of the impact resistance value, which is below remains in line with expectations, is seen.

In contrast to this, the inventively used, modified PBT resin a glycol component, which repeating units or part of the tetramethylene glycol forms, which is the linear glycol component, which is partially substituted with 2-substituted 1,3-propanediol

is tuiert, which represents a glycol component with a side chain. The presence of the side chain interrupts the regularity of the polymer chain and reduces according to the degree of crystallinity.

The modified PBT resin of the present invention thus has a much greater degree of non-crystalline phase and is believed to cause a polymer composition having a surprisingly high impact resistance

if suitably with a polycarbonate 30

resin is mixed.

The following examples illustrate the invention. In the examples, the term "parts" refers to

"Parts by weight". The properties of the resins were rated by 35

the following procedures are determined.

(1) Content of poly-2-methyl-1,3-propylene terephthalate

Content of poly-2-methyl-1,3-propylene terephthalate, as shown in Table 1 below, were calculated as mol% based on the nuclear magnetic resonance spectra (NMR).

The limiting viscosity number was at 25 ⁰ C in o-chlorine

(2) Limiting viscosity number The limiting viscosity is determined by phenol

¹⁰ (3) Melting point and heat of fusion

The Perkin Elmer Model DSC-1B Differential Scanning Calorimeter was used for this measurement. as

The standard used was the heat of fusion for Sn. 15th

(4) Relative degree of crystallinity

It became the peak area based on the melting of the resin, as obtained with a differential

tactile calorimeter, used. The peak area of PBT (Resin Ί in Table 1) was assigned the value of 100%.

(5) Tensile strength limit and tensile elongation at break 25

It became the Tensilon UTM-1-5000 B device from the company Toyo Baldwin Co. used, in accordance with the procedure described in ASTM D-638.

(6) Izod impact strength test

It became the company's Izod impact tester Toyo Seiki Seisakushyo Co. used. The procedure described in ASTM-D-256 was used for the notched test applied.

(7) Thermal deformation temperature The procedure described in ASTM D-648 was followed

used with a load of 18.56 kg / cm.

Production example 1

The PBT resin was prepared according to the following Process made.

A mixture of 194.0 parts of dimethyl terephthalate, 135.0 parts of tetramethylene glycol and 0.20 part of titanium tetrabutoxide catalyst was placed in a reactor equipped with a twin-screw belt-type stirrer. The reaction was continued for one hour at 180 ° C. in a nitrogen stream and under normal pressure. Thereafter, the reaction mixture over 2.5 hours at 23O ⁰ C was heated and distilled off methanol produced, wherein 90% of the theoretical

tables amount have been achieved. Thereafter, 0.02 parts tridecyl phosphite the reaction mixture was added and the reaction mixture temperature raised to 250 ⁰ C. The pressure within the reaction system was reduced to 0.2 mmHg over 40 minutes, and the polymerization was continued under these conditions for 3.5 hours.

Production example 2

The modified PBT resin was prepared according to the procedure below 30

described method produced.

A mixture of 194.0 parts of dimethyl terephthalate, 121.5 parts of tetramethylene glycol and 2-methyl-1,3-propane

diol and 0.20 parts of titanium tetrabutoxide catalyst if

placed in a reactor with a twin-screw Belt type stirrer was equipped.

- AH-

The reaction was continued for 1 hour at 180 ° C. in a stream of nitrogen and under normal pressure. The reaction mixture was then heated 2.5 hours 23O ⁰ C, with 90% of the theoretical amount of produced were distilled off methanol. Thereafter, 0.02 parts tridecyl phosphite the reaction mixture was added and the reaction mixture temperature raised to 250 ⁰ C. The pressure of the reaction system was reduced to 0.2 mmHg over 40 minutes, and the polymerization was 3.5 hours under them

^ Conditions continued.

Preparation examples 3 and 4

The modified PBT resins were made from various Proportions of tetramethylene glycol and 2-methyl-1,3-propanediol, as listed in Table 1 below, using that described in Preparation Example 2 Process produced.

The properties of the in Preparation Examples 1 to 4 obtained polymers and copolymers are shown in table.

33134A2

Table 1

ι
| A
'tieit admitted Dimethyl terephthalate parts Manufacturing examples 2 3 4th 10 Tetramethylene glycol | " 1 194.0 194.0 194.0 I.
2-methyl-1,3-propanediol "
i
I.
Tridecyl phosphite "
Tetrabutoxytitanium '"
I. 194.0 121.5 114.8 87.7 2-methyl-1 ^ -propylene tere
phthalate component | % 135.0 13.5
0.02
0.20 20.2
0.02
0.20 47.3
0.02
0.20 15th
20th Limiting viscosity number I dl / g
I. 0.02
0.20 12th 18th 47 I.
Melting point ι ⁰ C 0 0.72 0.74 0.83 relative ι
Degree of crystallinity% 0.82 213 189 141 25th 229 77 64 8th 100

Examples 1, 2 and 3 and Comparative Examples 1 and 2

The polyester and bisphenol A polycarbonate ("Lupilon", trade name, available from Mitsubishi Gas Kagaku Co., Ltd.) were air-dried at 60 ° C. for 8 hours. The dried ones Polymers were mixed with one another in the proportions listed in Table 2 below and added to them

20th 25th 30th

Mixtures were added with 0.4 parts of tridecyl phosphite. The mixtures were kneaded and extruded into pellets using an extruder equipped with a monoaxial screw from the full flying type (full-flight-type) having an inner diameter of 40 mm and was maintained at 230 to 25O ⁰ C. The resulting pellets were air-dried at 80 ° C for 8 hours and molded into test pieces using a standard injection molding machine at 52 ° C. The properties

^ of the compositions obtained are

listed in Table 2 below. The properties of the above-described polycarbonate and polyester (PBT resin) obtained in Production Example 1 are given as Reference Examples 1 and 2.

35

α
σ ι
I. Q) Polycarbonate parts ω
σι O 2 2 1 t— ·
cn P- ³
O example 40. 3 4th cn 2 I unit Ό Manufacturing ' Tabel 100 20th 2 2o 40 40 β
• Η example 1 " - hO
<ϋ C
ri D
• Η Xi (PBT resin) '
-2, " Reference example - - 60 - - - ω ο I. 1 80 +5 W Μ ο I ti - Comparative Il _j | ι · It - 80 60 1 Tensile Strength Limit, kg / cm 100 - - 328 - - 40 60 Tensile elongation '% 670 324 19.5 319 340 297 Impact resistance ι 87 12.5 21.0 24.3 60 34.5 (notched), kg / cm / c 5.4 »'(Not notched)'" - 62 4.1 light ge 6.1 8.3 15.2 1 540 light broke light ge light ge not ge thermal deforma- jo _c • 8th Broken 84 broke broke - broke tion temperature I 130 79 78 81 335 59 ta 2.7 1.7 44 2.8 55 40 85

The object of the present invention is to improve a blended polymer composition of polybutylene glycol and a polycarbonate defined as (II). This is achieved by using the Glycol component 1,3-propanediol with an alkyl group or alkyl groups in the 2-position. The previously known mixture of polybutylene glycol and polycarbonate (II), Listed as Comparative Example 1 is in terms of the thermal deformation temperature and the flexural strength or rigidity at high temperature improved compared to polybutylene glycol alone, however, the impact resistance is not improved to the desired extent. The present invention solves this problem and creates a mixture of polybutylene glycol and the polycarbonate (II) with unexpectedly improved impact resistance, while the high values with respect to the thermal deformation temperature and the tensile strength limit are maintained. From the The above results can be seen that the composition according to the invention is a mixture with excellent Properties that are balanced in all respects. Because it is required that the mixture has a high thermal deformation temperature, the mixture of Comparative Example 2 is the one has too low a thermal deformation temperature, not suitable.

30 35

Claims (2)

25 claims 1. Polymer composition, characterized in that it contains ³⁰ (I) 5 to 95% by weight of a polyester with terephthalic acid as the acid component and 1 to 25 mol% of a glycol of the formula (1) given below and 99 to 75 mol% of tetramethylene glycol as the glycol component, and 95 to 5 wt .-% of a polycarbonate of a di (monohydroxyphenyD-substituted, aliphatic hydrocarbon, • β HO-CH ₀ -C-CH ₀ -OH ά _χ ά R ₂ (1) wherein R ₁ and Rp each represent hydrogen or alkyl of 1 to 4 carbon atoms, provided that R ^ and Rp are not hydrogen at the same time. 10 2. Polymer composition according to claim 1, characterized ge indicates that the glycol of formula (1) is 2-methyl-1,3-propylene glycol.