CN104962048B8 - A kind of fiberglass reinforced fire retardant PBT material and preparation method thereof - Google Patents

Abstract

The invention provides a kind of fiberglass reinforced fire retardant PBT material and preparation method thereof, comprising PBT：40%～70%, fire-retardant master granule：18～30%, glass fibre：10～30%, glycidyl amine epoxy resin：0.1～0.5%, brucite：0.1～0.5%, other processing aids：0.5～1.0%, obtain the excellent enhancing flame-retardant PBT material of high CTI value, high-breakdown-voltage, mechanical performance, two-step method is taken to prepare, the first step uses double screw extruder, prepare fire retardant master batch, second step prepares enhancing flame-retardant PBT material again, and the PBT material can be used for electronic apparatus plastic.

Description

_A kind of glass fiber reinforced flame retardant PBT material and preparation method thereof

technical field

[0001] The present invention relates to the field of polymer materials, in particular to a glass fiber reinforced flame retardant PBT material.

Background technique

Reinforced flame retardant PBT material is widely used in electronic and electrical products, and electronic and electrical products require materials not only to have excellent mechanical properties, but also to have good electrical properties, especially the tracking index and breakdown voltage of the material. The index requirements are very high, and the flame retardants used in the PBT flame retardant system are mostly halogen-based flame retardants, but they are easy to precipitate from the surface of the material, corrode the mold, and can generate a large number of conductive ions and carbon particle deposits, which promotes current leakage. , greatly reducing the tracking index (hereinafter referred to as CTI) of the material, and the breakdown voltage of the material is not high, usually lower than 225V. In order to obtain glass fiber reinforced flame-retardant PBT materials with high CTI value and high breakdown voltage, phosphorus-based or nitrogen-based flame retardants are usually used to replace halogen-based flame retardants, or compounding methods are used to reduce the amount of halogen-based flame retardants. To achieve the purpose of improving the CTI value, the flame retardant efficiency of halogen-based flame retardants is optimal for PBT materials, and the required addition amount is relatively low, which provides the possibility to obtain high mechanical properties, so , The use of halogen flame retardants to flame retardant PBT, while requiring a higher CTI value and a higher breakdown voltage is an urgent technical problem to be solved.

SUMMARY OF THE INVENTION

[0003] In order to solve the above-mentioned technical problems, the present invention provides a kind of glass fiber reinforced flame-retardant PBT material and preparation method thereof.

A kind of glass fiber reinforced flame-retardant PBT material, comprises following component (percent by weight):

PBT: 40%～70%

Flame retardant master batch: 18～30%

Glass fiber: 1～30%

Glycidylamine epoxy resin: 0.1～0.5%

Hydrotalcite: 0.1～0.5%

Other processing aids: 0.5～1.0%

Described PBT intrinsic viscosity 0.7～1.3;

[0012] The flame retardant master batch includes a main flame retardant, a flame retardant synergist and a carrier resin. The main flame retardant is at least one of decabromodiphenylethane, brominated epoxy resin, brominated polystyrene and brominated polycarbonate, the flame retardant synergist is antimony trioxide, and the main flame retardant is The weight ratio of the flame retardant synergist is 3:1 or 2:1 or 4:1, the carrier resin is nylon 66 resin or nylon 6 resin, the weight percentage of the carrier resin in the flame retardant masterbatch is 30%, and the flame retardant masterbatch The weight ratio of the sum of the main flame retardant and the flame retardant synergist in the pellets is 70%;

Described glass fiber is the alkali-free glass fiber of monofilament diameter 10～15 μm;

Described glycidylamine epoxy resin is triglycidyl-p-aminophenol, tetraglycidyl-1,3-bisaminomethyl cyclohexane, N,N-diglycidyl-4-glycidyl oxygen At least one of aniline and diisopropylidene tetraglycidylamine; the effect of glycidylamine epoxy resin is to improve the CTI value of the material;

The specific surface area of described hydrotalcite＜15m / g, the effect of hydrotalcite is to improve CTI value, improve the breakdown voltage of material simultaneously;

[0016] The other processing aids include antioxidants and lubricants, such as commonly used antioxidant 1010, antioxidant 168, lubricant EBS;

A kind of preparation method of glass fiber reinforced flame-retardant PBT material, comprises two steps, and the first step is the preparation of flame-retardant master batch, and the second step is the blending extrusion of composite material, specifically as follows:

In the first step, PA66 resin, main flame retardant, flame retardant synergist are weighed according to the proportion, stirred 3～5 minutes in high-speed stirring pot, then join in twin-screw extruder and extrude, extruding temperature is 250~270 degrees, and the vacuum degree is 0.04~

0.08MPa, the flame retardant masterbatch is obtained by water-cooled pelletizing and packaging. The flame retardant masterbatch is placed in a blast dryer for subsequent use after drying, the drying temperature is 120 degrees, and the drying time is 4 to 6 hours.

[0019] The second step is to place the PBT resin in a blast dryer to dry, and the drying temperature is 120 degrees, and the drying time is 4 to 6 hours. PBT resin, flame retardant master batch are weighed proportionally and poured into the high-speed stirring pot and stirred for 1 to 2 minutes, poured into corresponding proportion of glycidyl amine epoxy resin, stirred for 1 to 2 minutes, and finally poured into corresponding proportion of hydrotalcite With other processing aids, stir for 1 to 2 minutes, add extrusion from the twin-screw main feed port, and add glass fiber from the twin-screw side feed port. The extrusion temperature is 230~250 degrees, the vacuum degree is 0.04~0.08MPa, and the glass fiber reinforced flame retardant PBT material is obtained by water-cooled pelletizing and packaging.

detailed description

The formula of comparative example 1～5 is following table 1:

Table 1: contrast 1～5 formula

[0022]

~~ Comparative Example I Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 One

~PBT Intrinsic Viscosity L O ~58 _ 58 - 58 58 58

Main flame retardant decabromodiphenyl ethyl 9 9

__^______

Wave Epoxy 9

__m______

Brominated polystyrene 9

__m______

Bromide polycarbonate 9

,.cool____________

Flame Retardant Synergist_Trioxide Ih Antimony 3___3_ 3 3__3

3. Fiberglass — 30 a 30 30 ~30 ~30 ~

I pill terbium antioxidant 1010 a 0.1 0.1 ~θ7ΐ 0.1 0.1

— —Antioxidant 168 0.1 — 0.1 0.1 ~θΓΐ ~0.1 ~

Έ slip agent I EBS I 0.1 I 0.1 0.1 I 0.1 I 0.1 ~

The formula of embodiment 1～5 is following table 2:

Table 2: embodiment 1～5 formula

[0025]

— Example 1 Example 2 Example 3 Example 4 Example 5 ~ Tbt Intrinsic viscosity 1.0 ~ 53 — 53 53 ~ 53 53

Έ Burning masterbatch one 17 17 17 ~Τ7 -17 ~

Fiberglass _ --one 30 30 ~30~30 ~30 —

One play oxygen agent _ antioxidant 1010 0.1 one 0.1 0.1 ~θΓΐ 0.1 ~

- Antioxidant 168 - 0.1 0.1 ~α I 0.1 0.1

Έ slip agent ~EBS 0.1 - 0.1 0.1 0.1 "ο.1 ~

Glycidamine οΠ 05 03 03

Epoxy resin _______

IjR Talc I 0.1 0.3 I 0.5

Decabromodiphenylethane in the flame-retardant master batch of embodiment 1: antimony trioxide: nylon 66 ratio is 9:3: 5; The brominated epoxy resin in the flame-retardant master batch of embodiment 2 : The ratio of antimony trioxide: nylon 66 is 9:3:5, and the glycidylamine epoxy resin is triglycidyl-p-aminophenol;

The brominated polystyrene in the flame-retardant master batch of embodiment 3: antimony trioxide: nylon 66 ratio is 9:3:5, and glycidylamine epoxy resin is tetraglycidol-1,3- bisaminomethylcyclohexane;

The brominated epoxy resin in the flame-retardant master batch of embodiment 4: antimony trioxide: nylon 66 ratio is 9:3:5, and glycidylamine epoxy resin is N, N-diglycidyl -4-glycidyl oxoaniline epoxy resin; the brominated polycarbonate in the flame retardant master batch of Example 5: antimony trioxide: nylon 66 ratio is 9:3:5, glycidylamine epoxy resin is diisopropylidene tetraglycidylamine;

Comparative example and embodiment detection result are following table 3:

Table 3: comparative example 1～5 and embodiment 1～5 detection data

[0031]

Test item Comparative Example Comparative Example Comparative Example Comparative Example

Bit ___________

La Zhongqiang 118 121 118 ~123 120 121 119 120 123 120

Degree/MPa___________

Ifiiiis195 200 205 198 200 200 198 202 203 199

Degree/MPa___________

Notched Impact ΪΤΤ4 1273 10.5 11.1 12.0 12.7 13.0 11.5 10.8 12.3 Impact Strength

/KJ/m2___________

Not missing U4θΠ 38?9 37\5 404 39?5 42?8 39?8 ΪΠ 442~ 38.9 Punch*strength

/KJ/m2____________

Flammability V-O V-O a V-O _ V-O V-O O V-O V-O a V-O V-O

CTI value Ϊ75 200 200 200 200 300 375 350 350 375

JV___________

Breakdown 30 32 32 32 32 32 32 45 45 45

H?: 3mm

/KV __________

Can find from the result of detection: flame retardant master batch, glycidyl amine epoxy resin and hydrotalcite can improve CTI value, especially hydrotalcite, not only can improve CTI value, also improve material breakdown voltage.

[0033] The conclusions drawn by other embodiments and corresponding comparative examples are all similar to the above. The PBT viscosity is 0.7~1.2, the glass fiber content is between 10~30%, the main flame retardant in the flame retardant masterbatch is several compounds or the carrier resin is nylon 6, which all show the rules obtained in Table 3.

Claims (7)

1. A glass fiber reinforced flame retardant PBT material, comprising the following components (weight percent): PBT: 40%~70% flame retardant masterbatch: 18~30% glass fiber: 10~30% glycidyl amine epoxy Resin: 0.1~0.5% Hydrotalcite: 0.1~0.5% Other processing aids: 0.5~1.0%. 2. glass fiber reinforced flame-retardant PBT material according to claim 1, is characterized in that, described PBT intrinsic viscosity is 0.7～1.3. 3. glass fiber reinforced flame retardant PBT material according to claim 1, is characterized in that, described flame retardant master batch comprises main fire retardant, fire retardant synergist and carrier resin; Main fire retardant is decabromine At least one of diphenylethane, brominated epoxy resin, brominated polystyrene and brominated polycarbonate, the flame retardant synergist is antimony trioxide, the weight of the main flame retardant and the flame retardant synergist The ratio is 3:1 or 2:1 or 4:1, the carrier resin is nylon 66 resin or nylon 6 resin, the weight percentage of carrier resin in the flame retardant masterbatch is 30%, and the main flame retardant and The weight ratio of the sum of the flame retardant synergists is 70%. 4. glass fiber reinforced flame-retardant PBT material according to claim 1, is characterized in that, described glass fiber is the alkali-free glass fiber of monofilament diameter 1～15 μΐΉ. 5. glass fiber reinforced flame-retardant PBT material according to claim 1, is characterized in that, described glycidyl amine epoxy resin is diglycidyl p-amino benzoic acid, tetraglycidyl-1,3-diamine At least one of methylcyclohexane, N,N-diglycidyl-4-glycidyloxyaniline, and diisopropylidene tetraglycidylamine. 6. glass fiber reinforced flame-retardant PBT material according to claim 1, is characterized in that, the specific surface area of described hydrotalcite is less than 15m / g. 7 . The glass fiber reinforced flame-retardant PBT material according to claim 1 , wherein the other processing aids include antioxidants and lubricants. 8 .