CN1039254A

CN1039254A - High-elastic rubber products gutta percha

Info

Publication number: CN1039254A
Application number: CN 88103978
Authority: CN
Inventors: 严瑞芳; 薛兆弘; 陈廷勇; 瞿文慧; 田秀兰
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 1988-07-04
Filing date: 1988-07-04
Publication date: 1990-01-31
Also published as: CN1013118B

Abstract

Guttapercha is the peculiar economic forest of China, the extract of gutta-percha tree, and resource is extremely abundant.The present invention system is a raw material with the guttapercha, adopts specific formula system to be made into the softish high elastic rubber, also can also can make the rubber item of unique properties with other blend rubbers as blending and modifying rubber.

Description

High-elastic rubber products gutta percha

The invention belongs to the development and use of natural polymer goods and materials, it is the economic forest that utilizes China's uniqueness, and the gum-type extract of gutta-percha tree is a kind of feature raw material, is used for preparing softish snappiness modified rubber goods.

The gutta-percha tree extract mainly contains two kinds, and the one, property of medicine composition, the one, resinoid.The latter at room temperature is a kind of hard solid.Because its good insulating always as insulating material such as undersea cables, also can be used as other plastics surrogates.Though making over cure to it, attempts in the past.But owing to do not break through on the vulcanization process, though also can only obtain stiff solid through sulfuration.The present invention ties up on the high-elastic gonosome vulcanization process of relevant patent (DE3227757) the synthesis of trans polyisoprene basis, and the alltrans feature according to contained poly double-olefin in the gutta-percha adopts improved vulcanization system, and it is sulfided into the high-elastic gonosome of softish.Because the good thermoplasticity (its extruder die size conservation rate is also higher than synthesis of trans polyisoprene) of guttapercha and the low batch mixing power consumption that possesses thus, high green strength etc., make when preparing vulcanized rubber by guttapercha, can be easy to adopt such as: extrude mold pressing, lamination, injection moulding, multiple mode such as blowing is processed into various difform goods.Another characteristics of this glue are that dynamic in-fighting is low, therefore, develop it and make tire product, and will be up-and-coming.Because the room temperature hardening of guttapercha, though hot workability is good, but cold operation is poor, in order to improve this performance, can on larger proportion, change the rubber accelerator consumption,, can make bark of eucommia vulcanization system at room temperature possess visco-elasticity as introducing the larger proportion cis-1,4-polybutadiene rubber, owing to make matrigel, guaranteed that also the rubber system has high intensity simultaneously with guttapercha.

The suitable prescription of the present invention when preparation guttapercha rubber item is: 100-20 parts of guttaperchas, rubber accelerator 0-80 part; Sulphur≤6 part, sulfur containing promoter≤4 part, ZnO≤4 part, MgO≤4 part, modifier≤10 part, stearic acid≤10 part, carbon black≤70 part, anti-aging agent≤3 part.

Above-mentioned system can with simple fabrication process common rubber processing with twin-roll machine on behind 70-110 ℃ of mixing, in 140-160 ℃ of heating, the rubber item that press vulcanization obtains requiring (is also availablely extruded mold pressing on press, lamination, injection moulding and blow molding obtain requiring the shape goods).

The natural bark of eucommia forest reserves of China are very abundant, present existing eucommia plantation's field boundary, area just has many places person more than thousand mu, developed rapidly again in recent years, but planting range has almost comprised the wide geographic area of economizing to Huanghe valley Shi Yu to the north of China Five Ridges, and can be on the hills, the mountain area plantation, discord grain strives ground.If develop this type of natural gum energetically, will already provide huge reserved resources (this work is subjected to common wealth fund commitee's Division of Chemistry and encourages and support) to China's rubber type

Embodiment 1:

Prescription: 100 parts of guttaperchas

Rubber accelerator ^*6 parts

2.5 parts in sulphur

Sulfur containing promoter ^*2.5 part

2 parts of ZnO

2 parts of MgO

55 parts of carbon blacks

Modifier ^{* * *}5 parts

5 parts of stearic acid

Anti-aging agent ^{* * *}1 part

Above-mentioned prescription is in that (this system has good extruder die size conservation rate and the film-forming properties that flows behind 70-100 ℃ of mixing on the twin-roll machine, therefore be suitable for extruding mold pressing, lamination, injection moulding, multiple molding modes such as blowing film forming) obtain requiring goods in 140-160 ℃ of press vulcanization.

Present embodiment gained mechanical property of vulcanized rubber:

Tensile strength 〉=180 kilograms per centimeter ²

Elongation at break 〉=400%

Residual set 〉=15%

300% tensile modulus＞120 kg/centimetre ²

*: rubber accelerator is introduced and is intended to make vulcanization system to be sulfided into effective cross-linking elasticity network, can use: natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, chloroprene rubber, isoprene-isobutylene rubber, ethylene-propylene rubber(EPR) etc. and polyester type, polyurethane-type, polyolefin-type thermoplastic elastomer.

* sulfur containing promoter: DM, M, TMTD, TMTT, TMTM, AZ, CZ, DZ

The introducing of * * modifier is intended to suppress effectively crystallization, can be: urethane resin, vibrin, resol, Resins, epoxy, polyamide resin, acrylic resin etc.

* * * anti-aging agent: anti-ageing, anti-old fourth, 4010 etc.

Embodiment 2:

Prescription: 55 parts of guttaperchas

Cis-1,4-polybutadiene rubber ^*45 parts

2.5 parts in sulphur

Sulfur containing promoter ^*2.5 part

2 parts of ZnO

2 parts of MgO

50 parts of carbon blacks

Modifier ^*5 parts

5 parts of stearic acid

1 part in anti-aging agent

Mechanical property when this system is not vulcanized and pure gutta-percha and the contrast of pure cis-butadiene cement:

Bark of eucommia system is not vulcanized in the pure cis-butadiene cement modification of pure gutta-percha

Tensile strength, kilograms per centimeter ²＞260＜10＞100

Elongation at break %＞500＜50＞200

Hardness＞98＜30-60

Feature hardness too high strength too soft and intensity are suitable

As seen this system had both overcome the very much not easy-operating shortcoming of pure gutta-percha room temperature hardness, and enough green strengths are arranged, and conveniently carried out various processing.This system on the twin-roll machine behind 70-100 ℃ of mixing, on press in 140-160 ℃ of heating and pressurizing (or other equipment) sulfuration, i.e. the goods that must ask.Its performance:

Tensile strength 〉=200 kilograms per centimeter ²

Elongation at break 〉=500%

Residual set 〉=20%

300% tensile modulus 〉=110 kilograms per centimeter ²

Annotate: used each * of (1) present embodiment, * *, * * *, * * * * symbol illustrates and enforcement

Example 1 is identical

(2) sulfur containing promoter scope 2-3 part; ZnO 1-2 part, 3-6 parts of modifiers; (because of producer originates different different)

(3) the used vulcanization system prescription of the present invention also is applicable to synthesis of trans-poly-isoamyl two

Alkene.

Claims

1, a kind of rubber item and method for making thereof, it is characterized in that with the guttapercha being that the workability prescription that the feature raw material is formed makes high-elastic rubber products through sulfuration processing, the compositing formula that is fit to is guttapercha 100-20 part, rubber accelerator 0-80 part, sulphur 0.5-6 part, sulfur containing promoter 0.5-4 part, ZnO0.5-4 part, MgO0.5-4 part, modifier 0.5-10 part, stearic acid 1-10 part, carbon black 20-70 part, anti-aging agent 1-3 part, its method for making are the raw material of this prescription to be mixed back on shaper heating and pressurizing sulfuration in 70-110 ℃ in common rubber processing on twin-roll machine obtain required rubber item.

2, rubber item as claimed in claim 1 and method for making thereof, be characterised in that said rubber accelerator is a natural rubber, cis-1,4-polybutadiene rubber, chloroprene rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, ethylene-propylene rubber(EPR) and polyester type, polyurethane-type, polyolefin-type thermoplastic elastomer, sulfur containing promoter is M, DM, TMTD, TMTM, TMTT, AZ, CZ, DZ, and modifier is polyamide resin, vibrin, urethane resin, resol, Resins, epoxy, acrylic resin.

3, as claim 1,2 described rubber item and method for makings thereof, it is characterized in that it is 100 parts of gutta-percha, 6 parts of rubber accelerators, 2.5 parts in sulphur, 2.5 parts of sulfur containing promoters, 2 parts of ZnO that its improvement sulfuration workability raw material is formed best proportioning, 55 parts of 2 parts of carbon blacks of MgO, 5 parts of modifiers, 5 parts of stearic acid, 1 part in anti-aging agent, this prescription is made multiple shape product through mixing sulfuration machine-shaping (extrude, mold pressing, lamination, injection moulding, blowing).

4, as claim 1,2 described rubber item and method for makings thereof, it is 55 parts of guttaperchas, 45 parts of cis-1,4-polybutadiene rubbers, 2.5 parts in sulphur, 2.5 parts of sulfur containing promoters, 2 parts of 2 parts of ZnO, MgO, 55 parts of carbon blacks, 5 parts of modifiers, 5 parts of stearic acid, 1 part in anti-aging agent that the optimum feed stock that it is characterized in that improving ease for operation in the manufacturing process is formed proportioning, this prescription through mix, sulfuration machine-shaping obtains product.

5, rubber item as claimed in claim 1 and method for making thereof is characterized in that best mixture temperature 80-100 ℃, and the optimum cure temperature is 140-160 ℃.

6, as claim 1,2, described rubber item and method for making thereof is characterized in that this vulcanization system prescription also is suitable for synthesis of trans-polyisoprene.