CN103087466A - Phenolic moulding plastic and preparation method thereof - Google Patents

Abstract

The invention discloses a phenolic moulding plastic and a preparation method of the phenolic moulding plastic. The phenolic moulding plastic comprises the following components in parts by weight: 100 parts of phenolic resin, 1 to 3 parts of urotropin, 3 to 8 parts of internal releasing agent, 10 to 20 parts of core-shell rubber particle, 30 to 50 parts of inorganic filler, 20 to 220 parts of reinforced fiber, and 1 to 4 parts of auxiliary, wherein the core-shell rubber particle comprises the raw materials composed of the following components in parts by weight: 100 parts of rubber particles, 1 to 5 parts of emulsifier, 10 to 50 parts of methyl methacrylate monomer, 10 to 80 parts of styrene monomer, and 1 to 3 parts of initiator. The phenolic moulding plastic has the advantages that the phenolic moulding plastic prepared by the preparation method of the phenolic moulding plastic, provided by the invention, mainly adopts the core-shell rubber as a toughening agent which can be mixed and cross-linked with the phenolic resin, so that the prepared product is higher in impacting strength and bending strength, and the vitrification transformation temperature and the volume resistivity cannot be obviously reduced.

Description

A kind of phenolaldehyde moulding compound and preparation method thereof

Technical field

The present invention relates to a kind of phenolaldehyde moulding compound and preparation method thereof, relate in particular to a kind of phenolaldehyde moulding compound that core shell rubbers toughner obtains and preparation method thereof that uses.

Background technology

Phenolaldehyde moulding compound (Phenolic Molding Compounds is referred to as PMC) mode of appearance is irregular solid particulate.By resol, mix various fillers, fiber reinforced material, urotropine, stablizer and pigment etc., form a kind of matrix material for compression moulding or injection moulding.

At present for phenolaldehyde moulding compound, three kinds of different method for toughening are arranged generally, namely polyvinyl butyral acetal is modified toughened, acrylonitrile butadiene rubber modified toughness reinforcing and nano-filler modified toughness reinforcing.

But existing three kinds of method for toughening have its shortcoming: use polyvinyl butyral acetal or acrylonitrile butadiene rubber modified, and all need to be to reduce second-order transition temperature as cost; Use nano-filler modifiedly, general addition should be controlled at below 2%, and too much add-on can cause the decline of composite materials property on the contrary, and this may be difficulty because minute breaking up of a large amount of nanoparticles in resin matrix becomes.

Summary of the invention

The purpose of this invention is to provide a kind of phenolaldehyde moulding compound and preparation method thereof, it mainly uses core shell rubbers toughner, then in conjunction with other material, to overcome the deficiency of mentioning in above-mentioned prior art.

For achieving the above object, the present invention is achieved through the following technical solutions:

A kind of phenolaldehyde moulding compound, the proportioning of feed composition is: 100 parts, resol, 1～3 part of urotropine, 3～8 parts of inner pattern releasing agent applicables, 10～20 parts of Core-shell rubber particles, 30～50 parts of mineral fillers, 20～220 parts of fortifying fibres, 1～4 part of auxiliary agent; The feed composition proportioning of wherein said Core-shell rubber particles is: 100 parts of rubber particles, 1～5 part of emulsifying agent, 10～50 parts of methyl methacrylate monomers, 10～80 parts of styrene monomers, 1～3 part of initiator; The preparation method of described Core-shell rubber particles is for to make by following steps:

A. prepare 100 parts of rubber particles, 95% particle diameter is controlled at below 1um;

B. add 1～5 part of emulsifying agent, 10～50 parts of methyl methacrylate monomers, 10～80 parts of styrene monomers, place approximately 15～30 minutes to swell rubber, then add 250～300 parts of entry;

C. add 1～3 part of initiator in the previous step mixture, put into emulsor and progressively be warming up to 90 degree, carry out conventional letex polymerization, about half an hour, make seed emulsion;

D. a certain amount of seed emulsion of weighing, put into whizzer, and with the speed operation of 12000 rev/mins 30 minutes, Dehydration got Core-shell rubber particles.

Described resol is solid-state novolak or resol resin.

Described inner pattern releasing agent applicable is stearate or wax.

Described mineral filler is the inertia ore powder, as mica powder, kaolin, calcium carbonate, aluminium hydroxide etc.

Described auxiliary agent is tinting material, softening agent etc.

Described fortifying fibre comprises glass fibre, vegetable fibre, chemical fibre etc.

Described rubber particle comprises divinyl rubber, paracril etc.

Described emulsifying agent comprises: anionic emulsifier, as AES, MS-1 etc.; Nonionic emulsifying agent is as OP-10 etc.

Described initiator comprises Potassium Persulphate, Sodium phosphate dibasic etc.

A kind of method for preparing above-mentioned phenolaldehyde moulding compound, make by following steps:

A. mix: resol is ground into less than 20 purpose fine powders;

B. with 100 parts, resol, 1～3 part of urotropine, 3～8 parts of inner pattern releasing agent applicables, 10～20 parts of Core-shell rubber particles, 30 ~ 50 parts of mineral fillers, 1～4 part of auxiliary agent uses stirrer to Uniform Dispersion;

C. two rollers or the screw machine of the powder after mixing by heating, add simultaneously 20～220 parts of fortifying fibres, make its melting and kneading, mixing even;

D. with kneading, mixing uniform material in previous step, through overcooling and pulverizing;

E. become granularity less than the irregular particle shape solid of 5mm through reciprocating sieve again.

Above feed composition all by weight.

Beneficial effect of the present invention is: the phenolaldehyde moulding compound that utilizes the preparation method of phenolaldehyde moulding compound of the present invention to obtain, owing to mainly having used core shell rubbers as toughner, this toughner can mix with resol crosslinked, utilize its product that makes to have than HI high impact and flexural strength, and can obviously not reduce second-order transition temperature and volume specific resistance.

In addition, at observed under electron microscope, after pre-designed core shell rubbers polymer particle and modified resin blend, its composition, form, size and the distribution in resin are constant before and after solidifying, and be namely irrelevant with solidification process.Use this core shell rubbers polymer particle not only can with the matrix resin crosslinking reaction, form the space reticulated structure in material, increased intensity, and can play certain shrinking agent effect, can not reduce the thermotolerance of material simultaneously.

Embodiment

Component	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					Resol	100	100	100	100
Urotropine	2	2	2	2
					Inner pattern releasing agent applicable	5	5	5	5
Mineral filler	45	45	45	45
					Core-shell rubber particles	10	15	20	0
Auxiliary agent	4	4	4	4
					Fortifying fibre	140	140	140	140

 

Above feed composition all by weight.

Embodiment 1:

Make phenolaldehyde moulding compound by following steps:

A. mix: resol is ground into less than 20 purpose fine powders;

B. with 100 parts, resol, 2 parts of urotropines, 5 parts of inner pattern releasing agent applicables, 10 parts of Core-shell rubber particles, 45 parts of mineral fillers, and 4 parts of auxiliary agents use stirrer to Uniform Dispersion;

C. two rollers or the screw machine of the powder after mixing by heating, add simultaneously 140 parts of fortifying fibres, make its melting and kneading, mixing even;

D. with kneading, mixing uniform material in previous step, through overcooling and pulverizing.

E. become granularity less than the irregular particle shape solid of 5mm through reciprocating sieve again.

The preparation method of above-mentioned Core-shell rubber particles is for to make by following steps:

A. prepare 100 parts of rubber particles, 95% particle diameter is controlled at below 1um;

B. add 3 parts of emulsifying agents, 30 parts of methyl methacrylate monomers, 40 parts of styrene monomers, place approximately 15 minutes to swell rubber, then add 280 parts of entry;

C. add 2 parts of initiators in the previous step mixture, put into emulsor and progressively be warming up to 90 degree, carry out conventional letex polymerization, about half an hour, make seed emulsion;

D. a certain amount of seed emulsion of weighing, put into whizzer, and with the speed operation of 12000 rev/mins 30 minutes, Dehydration got Core-shell rubber particles.

Obtain phenolaldehyde moulding compound of the present invention by above preparation process.

Embodiment 2:

Except Core-shell rubber particles quantity is 15 parts, other conditions and implementation step are all identical with embodiment 1.

Embodiment 3:

Except Core-shell rubber particles quantity is 20 parts, other conditions and implementation step are all identical with embodiment 1.

Embodiment 4:

Except Core-shell rubber particles quantity is 0 part, outside namely not adding, other conditions and implementation step are all identical with embodiment 1.

Be below the evaluating characteristics table of phenolaldehyde moulding compound in concrete application that makes by above-described embodiment, wherein the component on form right side is the component ratio of Core-shell rubber particles:

Test event

Testing standard

Unit

10 parts

15 parts

20 parts

Do not add

Shock strength

GBT 1043.1-2008

kJ/m 2

10

13

11

8

Flexural strength

GBT 1449-2005

MPa

200

210

220

190

Tensile strength

GBT 1040-2006

MPa

100

110

115

85

Shrinking percentage

ISO 2577-2007

%

0.24

0.20

0.14

0.30

Second-order transition temperature

ISO 11359-1999

℃

>260

>260

>260

>260

Volume resistance

GBT 1410-2006

Ω.m

>10 15

>10 15

>10 15

>10 15

All with the moulding of Transfer molding mode (with reference to ISO 10724-1998), actual conditions is as follows in the making of above-mentioned evaluating characteristics sample used:

Die temperature: 165-175 ℃

Injection pressure: 60 Mpa

Injection speed: 50-150mm/sec

Mold pressure: 120 Mpa

Inject time: 90 sec

Dwell time: 240 sec

The after fixing condition: 180 ℃, 8 hours.

Claims (3)

1. phenolaldehyde moulding compound, it is characterized in that: the proportioning of feed composition is: 100 parts, resol, 1～3 part of urotropine, 3～8 parts of inner pattern releasing agent applicables, 10～20 parts of Core-shell rubber particles, 30～50 parts of mineral fillers, 20～220 parts of fortifying fibres, 1～4 part of auxiliary agent; The feed composition proportioning of wherein said Core-shell rubber particles is: 100 parts of rubber particles, 1～5 part of emulsifying agent, 10～50 parts of methyl methacrylate monomers, 10～80 parts of styrene monomers, 1～3 part of initiator; The preparation method of described Core-shell rubber particles is for to make by following steps:

A. prepare 100 parts of rubber particles, 95% particle diameter is controlled at below 1um;

B. add 1～5 part of emulsifying agent, 10～50 parts of methyl methacrylate monomers, 10～80 parts of styrene monomers, place approximately 15～30 minutes to swell rubber, then add 250～300 parts of entry;

C. add 1～3 part of initiator in the previous step mixture, put into emulsor and progressively be warming up to 90 degree, carry out conventional letex polymerization, about half an hour, make seed emulsion;

D. a certain amount of seed emulsion of weighing, put into whizzer, and with the speed operation of 12000 rev/mins 30 minutes, Dehydration got Core-shell rubber particles.

2. phenolaldehyde moulding compound as claimed in claim 1, it is characterized in that: described mineral filler is the inertia ore powder.

3. method for preparing phenolaldehyde moulding compound as claimed in claim 1 is characterized in that: make by following steps:

A. mix: resol is ground into less than 20 purpose fine powders;

B. with 100 parts, resol, 1～3 part of urotropine, 3～8 parts of inner pattern releasing agent applicables, 10～20 parts of Core-shell rubber particles, 30 ~ 50 parts of mineral fillers, 1～4 part of auxiliary agent uses stirrer to Uniform Dispersion;

C. two rollers or the screw machine of the powder after mixing by heating, add simultaneously 20～220 parts of fortifying fibres, make its melting and kneading, mixing even;

D. with kneading, mixing uniform material in previous step, through overcooling and pulverizing;

E. become granularity less than the irregular particle shape solid of 5mm through reciprocating sieve again.