CN106046573A

CN106046573A - Composition with isotactic polybutylene-1 and dibasic acid metal salt nucleating agent and preparation of composition

Info

Publication number: CN106046573A
Application number: CN201610531956.3A
Authority: CN
Inventors: 李训刚; 王泽凡; 李向阳; 张建军; 毛晨曦; 王凯; 张鸿宇; 李少阳; 崔凯; 王冉; 刘凤玉; 巩翼龙; 代燕琴; 杨树竹; 张惠芳; 王朋仁; 王改敬; 王克智
Original assignee: SHANXI CHEMICAL RESEARCH INSTITUTE (CO LTD)
Current assignee: SHANXI CHEMICAL RESEARCH INSTITUTE (CO LTD)
Priority date: 2016-07-07
Filing date: 2016-07-07
Publication date: 2016-10-26

Abstract

The invention discloses a composition. The composition comprises 0.01-5 parts of the dibasic acid metal salt nucleating agent and 100 parts of the isotactic polybutylene-1. Dibasic acid metal salt is used as the nucleating agent, so that transformation of the isotactic polybutylene-1 in a crystal form II into isotactic polybutylene-1 in a crystal form I can be effectively accelerated. The composition has the advantages that the isotactic polybutylene-1 in the crystal form II can be quickly transformed into the isotactic polybutylene-1 in the crystal form I by means of preparation by the aid of equipment such as an extruding machine, an injection molding machine, an internal mixer, an open mill and a torque rheometer or conventional rubber and plastic processing technologies, and accordingly the composition with the isotactic polybutylene-1 in the stable crystal form I can be obtained and has important significance in the industry and business.

Description

A kind of compositions of isotactic PB Polybutene-1 and binary acid metallic salt nucleator and Preparation

Technical field

The present invention relates to a kind of promote the isotactic PB Polybutene-1 crystal formation II nucleator to crystal formation I and application thereof, belong to plastics Auxiliary agent and polymeric material field.

Technical background

Isotactic PB Polybutene-1 is a kind of high molecular inert polymer, has prominent heat-resisting, creep resistant, resistance to environment and answers Power cracking behavior and good toughness, be one of the most most advanced chemical material, be described as " plastics gold " abroad, It is suitable for making tubing, thin film and thin plate, especially optimal to make hot-water line.Although isotactic PB Polybutene-1 excellent performance, but very long adding The work cycle always restricts the key factor of its development.Tracing it to its cause and being because isotactic PB Polybutene-1 is a kind of heteromorphic polymer (include I, II, III, IV, V 5 kind, I type is most stable of, is also the crystal formation most with actually used value, and II type is heating power Learn labile state).

After melting under condition of normal pressure, during the cooling molding of isotactic PB Polybutene-1, firstly generate the crystal formation II of instability, this shape Under state, goods fusing point is low, soft, bad mechanical strength, unstable properties, easy stress deformation.The feelings that goods are not stressed in room temperature After standing 7-10 days under condition, crystal formation II can slowly be converted to crystal formation I, and now goods fusing point is high, hardness is high, mechanical strength improves, Stable performance.Crystal conversion process brings very big inconvenience to production and application the most slowly, therefore, the most directly or quickly obtains Crystal formation I that must be stable, the serviceability reaching optimal is one urgent problem of current research field.

Prior art yet there are no employing add nucleator to the method realizing the quick crystal conversion of isotactic PB Polybutene-1, also Have no nucleator and PB Polybutene-1 composite and the report of preparation thereof.

Summary of the invention

In order to solve the problems referred to above, it is an object of the invention to provide and a kind of accelerate the two of isotactic PB Polybutene-1 crystal conversion Unit's acid dihydrazide class nucleator, promotes isotactic PB Polybutene-1 crystal formation rapid conversion, to be suitable for large-scale commercial production and to answer With.Further object is that provide this isotactic PB Polybutene-1 and binary acid dihydrazide class nucleator compositions and It is prepared.

A kind of composition component of isotactic PB Polybutene-1 and binary acid dihydrazide class nucleator include isotactic PB Polybutene-1 and Binary acid dihydrazide class nucleator, including or do not include other on result of the present invention produce impact antioxidant, plasticizer, The auxiliary agents such as light stabilizer.

The structural formula of the nucleator binary acid slaine in said composition, as following formula (1) represents:

Formula (1)

In formula (1), R be expressed as alkylidene, sub-even thiazolinyl, have the alkylidene of ehter bond, replacement or unsubstituted cycloalkyl, replacement or Unsubstituted aryl, replacement or unsubstituted heterocycle, replacement or do not replace norborene, replacement or not substituted bicyclic heptane.Mⁿ⁺For gold Belong to ion, wherein: n is the integer of 1-3；m=3-n；When n is 1-2, x is 0, and when n is 3, x is 1.

Binary acid slaine nucleator described in said composition, the R in formula (1) for replace or unsubstituted cycloalkyl, Replace or unsubstituted aryl, replacement or unsubstituted heterocycle, replacement or do not replace norborene, the most unsubstituted cycloalkyl.

Binary acid slaine nucleator described in said composition, the M in formula (1)ⁿ⁺For the metal ion of 1-3 valency, excellent Elect bivalent metal ion as.

Binary acid metallic salt nucleator described in said composition accounts for isotactic PB Polybutene-1 weight in the composition 0.01%-5%, preferably 0.5%.

Said composition can pass through the equipment such as extruder, injection machine, banbury, mill, torque rheometer and conventional rubber Mould processing technique to prepare.

The invention have the characteristics that 1, pass through to add binary acid metallic salt nucleator in isotactic PB Polybutene-1, promote Rule PB Polybutene-1 crystal formation rapid conversion, the isotactic PB Polybutene-1 compositions obtaining having stable crystal form I being more prone to, in industry Significant with in business.2, use conventional rubber and plastic process equipment and technique to prepare said composition material, there is step letter The features such as list, easy operation.

Accompanying drawing explanation

Fig. 1. the crystal formation II of isotactic PB Polybutene-1 is schemed over time to the transformation conversion ratio of crystal formation I.

Detailed description of the invention

Below in conjunction with instantiation, the present invention will be further described in detail.

Embodiment

By isotactic PB Polybutene-1 (Shandong Orient Hongye Chemical Co. Ltd.), adjacent cyclohexyldicarboxylic acids calcium and antioxidant 215(is commercially available) empirically ratio (100:0.5:0.2) put into torque rheometer (the Shanghai Kechuang limited public affairs of rubber and plastics machine equipment Department) in mix homogeneously melting mixing (150 DEG C, 80rpm, 5min) cool down to be measured afterwards.

Comparative example

Comparative example of the present invention uses without the isotactic PB Polybutene-1 of nucleator neighbour's cyclohexyldicarboxylic acids calcium, Sample Preparation Procedure with Embodiment is consistent.

Embodiment in the present invention is tested under the same conditions with comparative example, all passes through differential scanning calorimeter (DSC) crystal formation II transformation to crystal formation I of isotactic PB Polybutene-1 is evaluated.Testing procedure is as follows:

Step one, the sample prepared is warming up to 160 DEG C with 40 DEG C/min after keep 3min eliminate thermal history, the coldest But to 25 DEG C, it is warming up to 160 DEG C with 5 DEG C/min by 25 DEG C the most again, tests its melting process, ask for the enthalpy of each melting peak. The melted enthalpy of crystal formation I is designated as H_Ⅰ, crystal formation II melts enthalpy and is designated as H_Ⅱ。

Step 2, test sample are warming up to 160 DEG C with 5 DEG C/min by 25 DEG C after placing certain time, test it and melt Journey, asks for the enthalpy of each melting peak.

Step 3, certain time will be placed every time after the melting peak enthalpy that records substitute into formula (1) and calculate crystal formation II to crystalline substance The conversion ratio of type I.

Conversion ratio=H_Ⅰ* 100/ (H_Ⅱ + ∆H_Ⅰ) formula (1)

Concrete test and result of calculation see table 1-2

The test of table 1 comparative example and result of calculation

Interval time (hour)	Conversion ratio (%)
		0	0
23	32.9852
		28	41.2681
44	85.29747

The test of table 2 embodiment and result of calculation

Interval time	Conversion ratio (%)
		0	0
23	62.74935
		28	86.75685
44	100

Concrete correlation curve such as Fig. 1.

Being contrasted with table 2 from table 1, within identical interval time, embodiment conversion ratio is higher than comparative example conversion ratio, says The crystal formation II of the isotactic PB Polybutene-1 in bright embodiment accelerates to the transition process of crystal formation I.And in FIG, reach a certain conversion During rate, the time used by embodiment is all shorter than comparative example, also demonstrates the crystal formation II of isotactic PB Polybutene-1 in embodiment to crystal formation I Change faster.Experiment shows, adds nucleator neighbour's cyclohexyldicarboxylic acids calcium and can effectively shorten the crystal formation of isotactic PB Polybutene-1 II, to the transformation cycle of crystal formation I, shortens the process-cycle simultaneously, and the extensively application to isotactic PB Polybutene-1 is significant.

The above is only the better embodiment of the present invention, thus all according to the structure described in present patent application scope, The equivalence that feature and principle are done changes or modifies, in the range of being all included in present patent application.

Claims

1. an isotactic PB Polybutene-1 and the compositions of binary acid metallic salt nucleator, it is characterised in that: described compositions group Divide and include isotactic PB Polybutene-1 and nucleator binary acid slaine.

Isotactic PB Polybutene-1 the most according to claim 1 and the compositions of binary acid metallic salt nucleator, its feature exists In, described compositions also includes the combination of one or more in antioxidant, plasticizer, light stabilizer.

Isotactic PB Polybutene-1 the most according to claim 1 and 2 and the compositions of binary acid metallic salt nucleator, its feature Being, the structural formula of described nucleator binary acid slaine, the most following formula of its feature (1) represents:

Formula (1)

In formula (1), R be expressed as alkylidene, sub-even thiazolinyl, have the alkylidene of ehter bond, replacement or unsubstituted cycloalkyl, replacement or Unsubstituted aryl, replacement or unsubstituted heterocycle, replacement or do not replace norborene, replacement or not substituted bicyclic heptane, Mⁿ⁺For gold Belong to ion, wherein: n is the integer of 1-3；m=3-n；When n is 1-2, x is 0, and when n is 3, x is 1.

Isotactic PB Polybutene-1 the most according to claim 3 and the compositions of binary acid metallic salt nucleator, its feature exists In, the R in described formula (1) is replacement or unsubstituted cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocycle, takes Generation or do not replace norborene.

Isotactic PB Polybutene-1 the most according to claim 3 and the compositions of binary acid metallic salt nucleator, its feature exists In, described binary acid slaine nucleator, it is characterised in that the M in formula (1)ⁿ⁺Metal ion for 1-3 valency.

Isotactic PB Polybutene-1 the most according to claim 3 and the compositions of binary acid metallic salt nucleator, its feature exists In, the R in described formula (1) is unsubstituted cycloalkyl, and Mn+ is the metal ion of divalent.

Isotactic PB Polybutene-1 the most according to claim 1 and 2 and the compositions of binary acid metallic salt nucleator, its feature Being, described nucleator binary acid slaine accounts for the 0.01%-5% of PB Polybutene-1 weight in the composition.

Isotactic PB Polybutene-1 the most according to claim 7 and the compositions of binary acid metallic salt nucleator, its feature exists In, described nucleator binary acid slaine account in the composition PB Polybutene-1 weight for 0.5%.

9. the preparation method of the compositions of the isotactic PB Polybutene-1 described in claim 1 or 2 and binary acid metallic salt nucleator, Said composition can pass through the equipment such as extruder, injection machine, banbury, mill, torque rheometer or conventional rubber and plastic processing work Prepared by skill.