RU2054023C1 - Polymeric adhesive - Google Patents

Abstract

FIELD: manufacture of adhesives. SUBSTANCE: the molten adhesive comprises (wt %): 0.1-3.0 unsaturated carboxylic acid dimide hydrocarbon derivatives of the general formula: C_nH_2n-mCl_m wherein n is >=12, m is 1-2 or R₁(C_nH_2n-1-mCl_m)_X wherein n is 1-3; X is 1-3; 0.5-5.0 R₁ aromatic hydrocarbon; 0.05-2.5 mineral paraffin hydrocarbon, synthetic polyolefinic wax, oxygen- containing derivatives or mixtures thereof, and polyolefin, the balance. When necessary, the adhesive may comprise 0.01-10.00% desired additives based of the weight of polyolefin. The properties are as follows: tensile strength 9.0-25.1 MPa, failure elongation 495-711 %, adhesion strength 11.1-15.8 kg/cm. EFFECT: improved properties of the polymeric adhesive. 2 cl, 1 tbl

Description

 The invention relates to polymer adhesives based on polyolefins used as hot melt adhesives or coatings applied in the form of a melt on various surfaces (metal, glass, ceramics, polymers).

The low adhesion of polyolefins, in particular to metals, is well known. One of the promising ways to improve the adhesion of polyolefins is their modification with small amounts of reactive low molecular weight additives, which, when forming an adhesive compound, migrating to the interface, provide the formation of chemical bonds between the polymer and the substrate. As such additives, peroxides [1] rosin and petroleum bitumen [2] dicarboxylic acids [3] as well as unsaturated dicarboxylic acid diimides [4] are used
The closest in technical essence to the adhesive according to the invention is a technical solution, according to which the adhesive composition contains high pressure polyethylene (100 parts by weight), N, N ^' meta-phenylenedimaleimide (0.25-3.10 parts by weight .), dihydroxybenzene (0.35-4.50 parts by weight) and, if necessary, anthracene 0.5-5.5 parts by weight) per 100 parts by weight. polyethylene [5]
However, this adhesive does not provide high strength adhesion, the order of which would correspond to the cohesive strength during shear of the polymer adhesive.

 The problem to which the invention is directed, is to increase the bond strength in adhesive joints.

The problem is solved by using a combination of unsaturated carboxylic acid diimide in a polyolefin-based polymer adhesive, hydrocarbon derivatives of the formula C _n H _2n-m Cl _m , where n ≥12, m 1-2 or
R ₁ (C _n H _2n-1 - _m Cl _m ) x where n 1-3, m 1-3, X 1-3, R ₁ aromatic hydrocarbon and mineral paraffin hydrocarbon, synthetic polyolefin wax, their oxygen-containing derivatives separately or their mixtures in various combinations in the following ratio of components, wt.

Unsaturated diimide
carboxylic acid 0.1-0.3
hydrocarbon derivatives 0.1-5.0
Mineral Paraffin
high hydrocarbon, synthetic
polyolefin
wax, their oxygen content
living derivatives or
mixtures thereof 0.05-2.5
Polyolefin Else
A chlorine-containing hydrocarbon is represented by the general formula C _n H _2n-m Cl _m , where n ≥ 1,2, m 1-2 or R ₁ (C _n H _2n-1-m Cl _m ) X, where n1-3, m 1- 3, X 1-3, R ₁ aromatic hydrocarbon.

 As a polyolefin, the adhesive contains an unsubstituted or substituted or grafted polyolefin, or mixtures thereof, preferably ethylene or propylene homopolymers; or a copolymer of ethylene and propylene; or a copolymer of ethylene and vinyl acetate; or a mixture of polyethylene (or a copolymer of ethylene with propylene) and a copolymer of ethylene with vinyl acetate; or polyethylene, polypropylene or a copolymer of ethylene and propylene with an unsaturated acid or unsaturated acid grafted thereon.

или диимидокислоту общей формулы, II:
R

N

R

N

R₃ где R₁,R₃= -CH=CH-,-CH₂-

-CH=

R₂ -(СН₂)-, где 1-6,

_,

_,

_,

R₄ C_2-6 алкил
R₅, R₆ H-, CH₃-.As the diimide, the adhesive contains an unsaturated acid diimide of the general formula I
R

or diimido acid of the general formula II:
R

N

R

N

R ₃ where R ₁ , R ₃ = -CH = CH -, - CH ₂ -

-Ch =

R ₂ - (CH ₂ ) -, where 1-6,

_,

_,

_,

R ₄ C _2-6 alkyl
R ₅ , R ₆ H-, CH ₃ -.

Preferred Diimides
N, N ^' metaphenylenedimaleimide, 4,4 ^' dithiophenyl maleimide,
1,6 hexamethylene dimaleimide.

Preferred hydrocarbon derivatives
1,4 di (trichloromethyl) benzene, chloroparaffin, chlorinated polyethylene.

As mineral paraffinic hydrocarbon polymer adhesive contains mineral paraffinic hydrocarbons having a drop point ^of 42-100 C, as the adhesive is a synthetic polyolefin wax comprises polyethylene, polypropylene wax, as oxygen-containing adhesive comprises stearic, palmitic or oleic acid, or amides, or oxidized polyethylene wax.

 If necessary, the target additives may be added to the adhesive: stabilizers, pigments, dyes, lubricants in an amount of 0.01-10.00% by weight of the polyolefin.

 A polymer adhesive is prepared by mixing all the components, followed by extrusion and granulation.

PRI me R 1. In a mixer of the type "drunk barrel" is mixed for 20 min granulated LDPE brand 10803-020 in the amount of 99.00 wt. (990 g), N, N ^' -metaphenylenedimaleimide 0.58 wt. (5.8 g), 1.4 di (trichloromethyl) benzene 0.28 wt. (2.8 g), polyethylene wax PV 300 0.07 wt. (0.70 g), air defense wax 30-0.07 wt. (0.70 g). Then the mixture is discharged into the batcher of the ZSK-30 twin-screw extruder (Werner und Pfleiderer company). The melt mixing time is 4-6 minutes. The extrusion temperature is 190-195 ^about C. The resulting mixture in the form of strands is cooled in a water bath and granulated.

 To measure polymer-metal adhesion, adhesive samples are pressed onto a metal substrate. As a substrate, plates with a size of 120x20x3 mm, made of steel 3, are used. The thickness of the polymer adhesive is 0.5-2.0 mm, fiberglass is used for reinforcement. The surface of the metal plates is pre-cleaned by sandblasting to a surface condition of Sa 2 1/2 according to the Swedish standard, and then degreased with alcohol.

Press mode: preheating duration up to 200 ^о С 10 min, heating under pressure 30 kgf / cm ² at 200 ^о С 5 min, cooling to 40-50 ^о С 20-30 min.

The adhesion is measured by peeling the reinforced adhesive from the substrate at an angle of 180 ^about at 20-25 ^about With GOST 411-77.

 Physico-mechanical properties (tensile strength and elongation at break) are determined on an Instron universal testing machine on type 5 samples (blades with a working part length of 40 ± 0.5 mm) according to GOST 11262-80 with a deformation rate of 20 mm / min

 The blades are cut with a stamp from plates 2 mm thick. Plates of polymer adhesive are obtained by thermal press in the same pressing mode as the samples for adhesion tests.

 PRI me R s 2-4, 6, 7, 9, 10-17. The polymer adhesive is prepared according to the method described in example 1. Information on the compositions of adhesives and the results of their tests are presented in the table.

PRI me R s 5-8. The polymer adhesive is prepared according to the procedure described in example 1, but the extrusion temperature of 220 ± 5 ^about C.

 The table shows the compositions and test results of the adhesive (examples 1-9), the compositions in accordance with the prototype (examples 10-13) and control compositions (examples 14-17).

 The presented results show that the polymer adhesive of the composition according to the invention significantly exceeds the known compositions of the prototype (15-100%) and control compositions in terms of adhesive bond strength with metals. Moreover, the variable components (diimide, chlorine-containing hydrocarbon, paraffin hydrocarbon) when used together provide a clear synergistic effect in adhesive properties (cf. Example 4 and Examples 14, 15, 17). The destruction of the samples of the claimed composition according to the invention occurs mainly cohesively in the adhesive polymer, which indicates that the adhesion to the metal exceeds the strength properties of the polymer.

 The invention can be used in various fields of technology, in particular, for mounting protective polymer coatings of polyolefins on metals in auto and agricultural machinery, for building structures, pipelines, as well as for the manufacture of multilayer materials, including polymers, metals, paper and other materials.

Claims (1)

1. POLYMERIC ADHESIVE containing a polyolefin and an unsaturated carboxylic acid diimide, characterized in that it further comprises hydrocarbon derivatives of the formula
C _n H _{2 n - m} Cl _m ,
where n ≥ 12;
m = 1 - 2,
or formulas
R ₁ (C _n H _{2 n - 1 - m} Cl _m ) _x ,
where n = 1 to 3;
m is 1 to 3;
x is 1 to 3;
R ₁ is an aromatic hydrocarbon,
and mineral paraffin hydrocarbon, synthetic polyolefin wax, their oxygen-containing derivatives or mixtures thereof in the following ratio of components, wt.%:
Unsaturated Carboxylic Acid Diimide - 0.1 - 3.0
These hydrocarbon derivatives are 0.1 to 5.0
Mineral paraffin hydrocarbon, synthetic polyolefin wax, their oxygen-containing derivatives or mixtures thereof - 0.05 - 2.5
Polyolefin - Else
2. The adhesive according to claim 1, characterized in that it further comprises target additives in an amount of 0.01 - 10.00% by weight of the polyolefin.

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